System and method for preventing or minimizing print defects in a printing process

文档序号：292133 发布日期：2021-11-23 浏览：25次中文

阅读说明：本技术 用于预防或最小化印刷过程中印刷缺陷的系统和方法 (System and method for preventing or minimizing print defects in a printing process ) 是由 H·切奇克 E·提罗什 G·芬克尔斯坦 L·萨波夫斯基 D·雷维于 2020-03-30 设计创作，主要内容包括：本公开提供了用于印刷的系统。本公开进一步提供了用于预防或最小化印刷过程中印刷缺陷的方法。(The present disclosure provides a system for printing. The present disclosure further provides methods for preventing or minimizing print defects during printing.)

1. A system for printing, comprising:

a liquid reservoir configured to hold a formulation comprising a first amount of at least one depletable chemical agent, the first amount being substantially equal to or greater than a predetermined threshold, wherein the formulation optionally further comprises at least one further component;

a replenishment reservoir configured to hold a second amount of the at least one depletable chemical, optionally in at least one liquid carrier,

a detection tool configured to identify at least: (i) whether the first amount of the depletable chemical agent decreases below the predetermined threshold and/or (ii) a functional capacity of the at least one depletable chemical agent decreases;

a transfer means configured to transfer at least a portion of the second amount of the at least one depletable chemical agent from the replenishment reservoir to the liquid reservoir once the reduction has been identified, optionally wherein the transfer means is a manual means.

2. The system of claim 1, wherein the detection tool is configured to measure and/or calculate the reduction.

3. The system of claim 1 or 2, wherein the detection tool is configured to record and/or report the reduction.

4. The system according to any one of claims 1 to 3, wherein the detection means is configured to activate the transfer means once the reduction has been identified.

5. The system according to any one of claims 1 to 4, wherein the system further comprises a control unit configured to control replenishment of the at least one depletable chemical agent in the liquid reservoir and optionally configured to activate the transfer means once the reduction has been identified.

6. The system of claim 5, wherein the system further comprises a communication means configured to transfer data/information between the detection means to the control unit.

7. The system of any one of claims 1 to 6, wherein the transfer tool is selected from a pressure-based tool, a jetting tool, a spraying tool, or a gravity tool.

8. The system of any one of claims 1 to 7, wherein the system further comprises at least one printing liquid reservoir configured to hold a printing liquid, wherein the printing liquid is optionally an ink and more optionally a water-based ink.

9. The system of any one of claims 1 to 8, wherein the system is used for indirect printing.

10. The system of claim 9, wherein the system further comprises an intermediate transfer member.

11. The system according to any one of claims 8 to 10, wherein the formulation is a treatment formulation configured for application onto at least one area of a release surface of the intermediate transfer member and forming a coating thereon.

12. The system of claim 11, wherein the formulation is applied to the release surface before the printing liquid is applied to the release surface.

13. The system of any one of claims 1 to 12, wherein the at least one depletable chemical agent is present in liquid form in the replenishment reservoir and wherein the replenishment reservoir and liquid reservoir are in liquid communication, thereby allowing transfer of at least a portion of the second amount of the at least one depletable chemical agent from the replenishment reservoir to the liquid reservoir once the reduction has been identified.

14. The system of claim 13, wherein the transfer means further comprises a regulating means configured to regulate the amount of transfer of the depletable chemical from the replenishment reservoir to the liquid reservoir and/or to avoid a reverse flow of liquid from the liquid reservoir to the replenishment reservoir.

15. The system of claim 14, wherein the conditioning means comprises at least one safety valve that allows one-way flow of liquid from the refill reservoir to the liquid reservoir.

16. The system of any one of claims 1 to 15, wherein the second amount of the at least one depletable chemical in the replenishment reservoir is greater than the first amount of the at least one depletable chemical in the liquid reservoir.

17. The system of any one of claims 1 to 16, wherein the system optionally further comprises a mixing tool configured to mix the at least one depletable chemical agent in the liquid reservoir and/or a replenishment reservoir.

18. The system of any one of claims 1 to 17, wherein the at least one depletable chemical agent in the replenishment reservoir is present in solid form.

19. The system of claim 18, wherein the system optionally further comprises a tool configured to mix, dissolve, or disperse the solid depletable chemical agent.

20. The system of claim 18 or 19, wherein the system optionally further comprises a heating means configured to assist in solubilizing the solid-exhaustible chemical agent.

21. The system according to any one of claims 1 to 20, wherein after detecting/identifying the reduction, the control unit is configured to control replenishment of the at least one exhaustible chemical agent in the liquid reservoir according to a replenishment profile selected for increasing the amount of the exhaustible chemical agent in the liquid reservoir to reach a value substantially equal to or greater than the predetermined threshold.

22. The system of any one of claims 1 to 21, wherein the system further comprises a processing utility.

23. The system of claim 22, wherein the processing utility is configured to provide a signal indication to a user indicating a need to replenish the at least one depletable chemical agent in the liquid reservoir after the reduction is identified.

24. The system according to any one of claims 1 to 23, wherein the system optionally further comprises means for stopping the printing process and resuming the printing process once replenishment is achieved/completed.

25. The system of any one of claims 21 to 24, wherein the supplemental spectrum defines one or more of: an amount of the at least one depletable chemical to be transferred from the replenishment reservoir to the liquid reservoir; the frequency of the supplement; the duration of the transfer; the manner of the transfer; the transfer rate.

26. The system of any one of claims 21 to 25, wherein the supplemental spectrum is determined based on one or more of: the first and/or second amount of the depletable chemical; the extent of said reduction; the relative amount of the depletable chemical relative to the amount of the formulation or the amount of the other component or components contained within the formulation.

27. The system of any one of claims 21 to 26, wherein the supplemental spectra are defined based on one or more of the printing conditions.

28. The system according to any one of claims 22 to 27, wherein the processing utility is configured to process images produced by the system and evaluate image print quality thereof, wherein the control unit is configured to cause replenishment of the at least one depletable chemical in the liquid reservoir when the image print quality is below a predetermined required amount.

29. The system of claim 28, wherein the processing utility is configured to generate an output indicative of the quality of the image, wherein the control unit is configured to cause replenishment of the at least one depletable chemical agent in the liquid reservoir when the output is below a predetermined threshold parameter.

30. The system of claim 29, wherein the processing unit is configured to display the output on a visual display unit, an audio device, or a combination thereof.

31. The system of claim 29, wherein the predetermined threshold parameter comprises a substantially different value or range of values representative of a desired printed image quality.

32. The system of any one of claims 29 to 31, wherein when the output is below a predetermined threshold parameter value, the system is optionally configured to immediately alert a user to stop or automatically stop the printing process, and optionally to resume the printing process once replenishment of the depletable chemical in the liquid reservoir is complete.

33. The system of any of claims 29 to 32, wherein the output reflects a value indicative of a granularity of the image.

34. The system of any one of claims 1 to 33, further comprising a user interface.

35. The system of claim 34, wherein the user interface is configured to allow a user to introduce one or more desired printing conditions for a printing process into the processing utility.

36. The system of any one of claims 1 to 35, further comprising a memory.

37. The system of claim 36, wherein the memory comprises a database of one or more image quality predetermined threshold parameters of a printing process.

38. The system of claim 36 or 37, wherein the processing utility is configured to correlate the image quality predetermined threshold parameter from the database with the output.

39. The system of any one of claims 1 to 38, wherein the system further comprises a tool to record replenishment history.

40. The system of any one of claims 1 to 39, wherein the detection tool is selected from a visual tool, a spectroscopic tool, a spectrophotometric tool, an electronic tool, a chemical tool, a physical tool, a print quality based tool, or any combination thereof.

41. The system of claim 40, wherein the tool is configured to detect/measure an amount of the at least one depletable chemical in the liquid reservoir, and wherein the system is configured to calculate a reduction in the first amount of the at least one depletable chemical based on the detected/measured amount.

42. The system of any one of claims 1 to 41, wherein the system further comprises a sampling unit configured to withdraw an aliquot of the formulation from the liquid reservoir for further analysis.

43. The system according to claim 42, wherein the sampling unit is configured to withdraw an aliquot of the formulation from the liquid reservoir as needed and/or at predetermined time intervals and/or after a predetermined number of printing cycles.

44. The system of any one of claims 1 to 43, wherein the reduction of the first amount of the depletable chemical agent is relative to an amount of another component or components of the formulation.

45. The system of any one of claims 1 to 44, wherein the reduction of the first amount of the depletable chemical occurs as a result of an undesired side reaction of the depletable chemical.

46. The system of claim 45, wherein the undesirable side reaction of the depletable chemical agent results in the formation of an undesirable byproduct in the liquid reservoir, and wherein the system optionally further comprises a tool configured to remove the byproduct.

47. The system of claim 46, wherein the system further comprises means for detecting the formation of and optionally measuring/determining the amount of said undesired by-products in said liquid reservoir.

48. The system of claim 47, wherein the system further comprises a tool configured to correlate the detected formation of the undesirable byproducts with the reduction of the first amount of the depletable chemical.

49. The system of any one of claims 1 to 48, wherein the reduction of the first amount of the depletable chemical is due to contamination of the formulation in the liquid reservoir with at least one contaminant, and wherein formation of at least one undesirable byproduct is due to interaction between the at least one depletable chemical and at least one contaminant.

50. The system of any one of claims 1 to 49, wherein the system further comprises at least one printing liquid reservoir configured to hold a printing liquid, optionally the printing liquid is an ink formulation, and wherein the reduction in the first amount of the depletable chemical is due to printing liquid contamination in the liquid reservoir.

51. The system of claim 50, wherein the printing liquid is an ink and comprises at least one binder and at least one colorant, and wherein the reduction of the first amount of the depletable chemical is due to an undesired side reaction of the depletable chemical with the at least one binder.

52. The system of any one of claims 1 to 51, wherein the system further comprises a protection unit configured to protect the liquid reservoir from contamination, such as ink contamination.

53. The system of any one of claims 1 to 52, wherein the system optionally further comprises a measuring means configured to measure the volume of the liquid in the liquid reservoir, wherein when the measured volume is below a predetermined minimum volume, the system is configured to instruct a user to refill the liquid reservoir with an additional amount of liquid formulation.

54. The system of any one of claims 1 to 53, wherein the system optionally further comprises a measuring means configured to measure an amount (e.g., volume/liquid or weight/solid) of the depletable chemical in the replenishment reservoir, wherein when the measured amount is below a predetermined minimum amount, the control unit is configured to instruct a user to refill the replenishment reservoir with a further amount of the depletable chemical.

55. The system of any one of claims 1 to 54, wherein the depletable chemical agent is a polymer agent containing an amine nitrogen atom in a plurality of functional groups, which need not be identical and can be combined.

56. The system of claim 55, wherein the polymer has a relatively high charge density.

57. The system of claim 55 or 56, wherein the molecular weight of the polymer is equal to or greater than 10,000 g/mole.

58. The system of any one of claims 1-57, wherein the depletable chemical is a polymer agent having at least one of: (a) a positive charge density of at least 3meq/g of said agent and an average molecular weight of at least 5,000, (b) a positive charge density of at least 6meq/g of said agent and an average molecular weight of at least 1,000, (c) a nitrogen content of at least 1% by weight and an average molecular weight of at least 50,000, and (d) a nitrogen content of at least 18% by weight and an average molecular weight of at least 10,000.

59. The system according to any one of claims 1 to 58, wherein the depletable chemical agent is a polymer agent having a density of positive charges.

60. The system of claim 59, wherein the positive charge density is at least 0.5meq/g, at least 1meq/g, at least 2meq/g, at least 3meq/g, at least 4meq/g, at least 5meq/g,6meq/g, at least 7meq/g, at least 8meq/g, at least 9meq/g, at least 10meq/g, at least 11meq/g, at least 12meq/g, at least 13meq/g, at least 14meq/g, at least 15meq/g, at least 16meq/g, at least 17meq/g, at least 18meq/g, at least 19meq/g, or at least 20meq/g of the agent.

61. The system of any one of claims 1 to 60, wherein the depletable chemical agent is a polymeric agent having an average molecular weight of at least 500, at least 800, at least 1,000, at least 1,300, at least 1,700, at least 2,000, at least 2,500, at least 3,000, at least 3,500, at least 4,000, at least 4,500, at least 5,000, at least 10,000, at least 15,000, at least 20,000, at least 25,000, at least 50,000, at least 100,000, at least 150,000, at least 200,000, at least 250,000, at least 500,000, at least 750,000, at least 1,000,000, or at least 2,000,000.

62. The system of any one of claims 1 to 61, wherein the depletable chemical agent is a polymer agent having an average molecular weight of at least 2,000, at least 10,000, or at least 25,000.

63. The system of any one of claims 1 to 62, wherein the depletable chemical agent comprises one or more nitrogen atoms that can be positively charged.

64. The system of claim 63, wherein the one or more nitrogen atoms constitute at least 1 wt.%, at least 1.4 wt.%, at least 2 wt.%, at least 5 wt.%, at least 8 wt.%, at least 10 wt.%, at least 15 wt.%, at least 18 wt.%, at least 20 wt.%, at least 24 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, or at least 50 wt.% of the depletable chemical agent.

65. The system of any one of claims 1 to 64, wherein the depletable chemical is a composition comprising poly (diallyldimethylammonium chloride)A polymeric agent of units.

66. The system of any one of claims 1 to 64, wherein the depletable chemical agent is a chemical comprising polyallylamineA polymeric agent of units.

67. The system of any one of claims 1 to 64, wherein the depletable chemical is a composition comprising poly (4-vinylpyridine)A polymeric agent of units.

68. The system of any one of claims 1-67, wherein the depletable chemical polymer agent is selected from the group consisting of: linear polyethylenimine, branched polyethylenimine, modified polyethylenimine, poly (diallyldimethylammonium chloride), poly (4-vinylpyridine), polyallylamine, vinylpyrrolidone-dimethylaminopropylmethacrylamide copolymer (Viviprint 131), vinylcaprolactam-dimethylaminopropylmethacrylamide hydroxyethyl methacrylate copolymer (Viviprint 200), vinylpyrrolidone and quaternized copolymer of dimethylaminoethyl methacrylate with diethyl sulfate (Viviprint 650), guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride.

69. The system of claim 68, wherein the depletable chemical polymer agent is Polyethyleneimine (PEI).

70. The system of any one of claims 1 to 69, wherein the first amount of the depletable chemical polymer agent in the formulation in the liquid reservoir is equal to or less than about 5, 4,3, 2, 1, 0.5, 0.4, 0.3, 0.2, 0.1, or equal to or at least about 0.05, or sometimes at least about 0.01% by weight.

71. The system of any one of claims 1-70, wherein the depletable chemical polymer agent is a polymer agent that is PEI and wherein the predetermined threshold is at least 0.01 wt%, at least 0.05 wt%, at least 0.10 wt%, at least 0.15 wt%, or at least 0.20 wt%.

72. The system of any one of claims 1 to 71, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein the first amount thereof in the liquid receptacle is a concentration by weight of at most 6%, at most 5%, at most 4%, at most 3%, at most 2.5%, at most 2.0%.

73. The system of any one of claims 1 to 72, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein the first amount thereof in the liquid receptacle is a concentration by weight that is in a range of 0.01 to 1%, 0.01 to 0.8%, 0.01 to 0.7%, 0.01 to 0.6%, 0.01 to 0.5%, 0.2 to 0.7%, 0.2 to 0.6%, or 0.2 to 0.5%.

74. The system of any one of claims 1 to 73, wherein said at least one depletable chemical is PEI, wherein said first amount thereof in said formulation in liquid reservoir is 0.25% by weight and said second amount thereof in said replenishment reservoir is 25% by weight in water.

75. The system of claim 74, wherein when the first amount of the PEI in the liquid receptacle decreases below a predetermined threshold of 0.01 wt%, the system is configured to transfer a portion of the second amount of the PEI from the replenishment receptacle to the liquid receptacle, thereby replenishing the amount of the PEI in the liquid receptacle to a value equal to or above the predetermined threshold (0.01 wt%) or replenishing the amount of the PEI in the liquid receptacle to a value equal to first amount (0.25 wt%).

76. The system of any one of claims 1 to 75, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein its average molecular weight is at least 20,000, at least 50,000, at least 100,000, at least 200,000, at least 350,000, at least 500,000, at least 700,000, at least 750,000, and optionally at most 3,000,000, at most 2,500,000, or at most 2,000,000.

77. The system of any one of claims 1 to 76, wherein the depletable chemical agent is a polymeric agent that is PEI, and wherein the PEI is a surfactant, a wetting agent, an anchoring agent, or any combination thereof.

78. The system of any one of claims 1 to 77, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the charge density of the PEI polymer is in the range of 16-20meq/g material.

79. The system of any one of claims 1 to 77, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the charge density of the PEI polymer is 8 meq/g.

80. The system of any one of claims 1 to 79, wherein the depletable chemical is silicone-functionalized PEI.

81. The system of any one of claims 1 to 80, wherein the depletable chemical agent is a quaternary ammonium compound.

82. The system of claim 81, wherein the quaternary ammonium compound is Larostat264A (BASF).

83. A system according to claim 81, wherein the quaternary ammonium compound is Foamquat SAQ (linoleamidopropyl ethyl dimethyl ammonium ethyl sulphate 90).

84. The system of any one of claims 1 to 83, wherein the depletable chemical is water dispersible.

85. The system of any one of claims 1 to 83, wherein the depletable chemical is water soluble.

86. The system of any one of claims 1 to 85, wherein the depletable chemical is a solid at room temperature.

87. The system according to any one of claims 51 to 86, wherein the at least one binder in the ink is an anionic binder.

88. The system of claim 87, wherein the anionic binder is an acrylic binder and/or a sulfonic acid binder.

89. The system of any one of claims 51 to 88, wherein the at least one binder in the ink is a negatively charged organic polymer resin.

90. The system of claim 89, wherein the negatively charged organic polymer resin has an average molecular weight of at least 8,000.

91. The system of claim 89 or 90, wherein the at least one binder in the ink is an acrylic polymer and/or an acrylic-styrene copolymer.

92. The system of any one of claims 51-91, wherein the adhesive is Joncryl 538 BASF.

93. The system of any one of claims 51 to 92, wherein said exhaustible chemical agent is PEI, and wherein said reduction of said first amount of PEI is due to undesired side reactions thereof with said at least one binder.

94. The system of any one of claims 1 to 93, wherein the system further comprises means for detecting, measuring or calculating the concentration of the depletable chemical agent in the formulation contained within the liquid reservoir and calculating therefrom the reduction in the first amount of the depletable chemical agent.

95. The system of claim 94, wherein the depletable chemical is PEI.

96. The system of claim 94, wherein said tool is a spectroscopic tool configured to detect said PEI based on the reaction of copper with said PEI.

97. The system of any of claims 1-96, wherein the printing system is an indirect printing system, the system further comprising:

i. an Intermediate Transfer Member (ITM) comprising a release layer surface;

a treatment station comprising a liquid receptacle configured for holding an aqueous treatment formulation as disclosed herein, the treatment station configured for applying the aqueous treatment formulation to a release layer surface of the ITM to form a treatment layer thereon;

a replenishment unit comprising a replenishment reservoir as disclosed herein.

An image forming station configured to apply a printing liquid to form an image on an aqueous treatment formulation formed on the intermediate transfer member;

v. a transfer station for transferring the image onto the printing substrate, for example by pressure contact between the ITM and the printing substrate.

98. The system of claim 97, wherein the printing liquid is an ink, optionally applied by jetting, and the system further comprises:

a drying station configured to at least partially dry the ink on the aqueous treatment formulation formed on the intermediate transfer member to produce an ink-image residue; and optionally drying means for drying the aqueous treatment formulation.

99. The system of any one of claims 11 to 98, wherein the treatment formulation comprises:

at least one water-soluble polymer;

at least one particulate material selected from: (i) at least one thermoplastic polymer particulate material, optionally in the form of an emulsion and/or dispersion; (ii) at least one thermosetting polymeric particulate material, optionally in the form of a dispersion and/or emulsion; or (iii) combinations thereof;

an aqueous carrier liquid; and

optionally, one or more of the following: (a) at least one humectant; (b) at least one surfactant and (c) at least one wetting agent.

100. The system of claim 99, wherein the treatment formulation further comprises at least one wetting agent.

101. The system of claim 100, wherein the wetting agent is PEI.

102. The system of claim 99, wherein the water soluble polymer is at least one modified polysaccharide.

103. The system of claim 102, wherein the modified polysaccharide is selected from a cellulose derivative, a cellulose ether, a methylcellulose, a hydroxypropyl methylcellulose, or any combination thereof.

104. The system of claim 103, wherein the modified polysaccharide is hydroxypropyl methylcellulose.

105. The system according to any one of claims 1 to 104, wherein the treatment formulation is as disclosed and exemplified herein.

106. A method for preventing or minimizing print defects in a printing process, wherein the print defects are associated with a reduction in a first amount of at least one depletable chemical agent contained within a liquid formulation (optionally in a liquid carrier), the method comprising:

identifying/detecting whether the first amount of the at least one depletable chemical agent decreases below a predetermined threshold and/or relative to the amount of at least one other component in the formulation; and

after identifying/detecting the reduction, adding a second amount of at least a portion of the at least one depletable chemical to the formulation, wherein the second amount of the at least a portion is sufficient to reestablish the first amount of the depletable chemical in the liquid formulation to be substantially equal to or greater than the predetermined threshold and/or wherein the second amount of the at least a portion is sufficient to offset the reduction of the first amount relative to the amount of at least another component in the formulation, thereby preventing or minimizing the print defect.

107. The method of claim 106, wherein the second amount of the at least one depletable chemical is provided in liquid form.

108. The method of claim 106, wherein the second amount of the at least one depletable chemical agent is provided in solid form.

109. The method of any one of claims 106 to 108, wherein the method further comprises mixing the at least a portion of the second amount of the at least one exhaustible chemical agent in the liquid formulation.

110. The method of claim 108, further comprising dissolving or dispersing a solid depletable chemical agent in at least one liquid carrier (which may be the same or different from the liquid carrier of the liquid formulation).

111. The method of claim 110, further comprising heating the solid depletable chemical to aid in its dissolution.

112. The method of any one of claims 106 to 111, wherein the liquid formulation is configured to be applied to a substrate on which an image is to be printed, or to an intermediate transfer member in an indirect printing process.

113. The method of any one of claims 106 to 112, wherein the method further comprises:

i. providing an Intermediate Transfer Member (ITM);

providing a treatment formulation;

applying the treatment formulation onto the image receiving surface of the ITM to form a wet treatment layer;

at least partially drying the wet treated layer to form an at least partially dried treated layer;

v. applying a printing liquid onto the at least partially dried treatment layer to form an image;

transferring the image onto a printing substrate by pressurized contact between the surface of the ITM and the printing substrate.

114. The method of claim 113, wherein the printing liquid is an ink, optionally an aqueous ink and the method further comprises:

applying ink drops on the at least partially dried treatment layer to form an ink image; and

at least partially drying the wet ink image on the aqueous treatment layer to form a partially dried ink image film to be transferred to the printing substrate.

115. The method of any one of claims 106 to 114, wherein the adding of the second amount of at least a portion of the at least one exhaustible chemical agent is performed according to a predetermined replenishment spectrum selected for increasing the amount of the exhaustible chemical agent in the liquid formulation, to reach a value substantially equal to or greater than a predetermined threshold value.

116. The method of any one of claims 106 to 115, wherein the method further comprises identifying a decrease in the first amount of the at least one exhaustible chemical agent relative to the amount of at least one other component in the formulation and providing a signal indicative of a need to add the at least one exhaustible chemical agent to the liquid formulation, thereby re-establishing the first amount of the exhaustible chemical agent in the liquid formulation to be substantially equal to or greater than the predetermined threshold value, thereby counteracting the decrease.

117. The method of claim 116, wherein the supplemental spectrum is a predetermined spectrum determined based on one or more of the printing conditions.

118. The method of any one of claims 106 to 117, wherein the method further comprises processing an image produced in the method and assessing image print quality thereof, wherein when the image print quality is below a predetermined desired quality, the method comprises adding at least a portion of the second amount of the at least one depletable chemical agent to the liquid formulation.

119. The method of claim 118, wherein the method includes generating an output indicative of the image quality, wherein when the output is below a predetermined threshold parameter, the method includes adding the at least a portion of the second amount of the at least one exhaustible chemical agent to the liquid formulation.

120. The method of claim 119, wherein the method comprises displaying the output on a visual display unit, an audio device, or a combination thereof.

121. The method of claim 119 or 120, wherein the output reflects a value indicative of a granularity of the image.

122. The method of claim 119, wherein the predetermined threshold parameter comprises a substantially different value or range of values representative of a desired printed image quality.

123. The method of any one of claims 106 to 122, further comprising identifying whether the first amount of the at least one depletable chemical agent decreases below a predetermined threshold, wherein the identifying is accomplished by a detection tool selected from a visual tool, a spectroscopic tool, a spectrophotometric measuring tool, an electronic tool, a chemical tool, a physical tool, a print quality based tool, or any combination thereof, and wherein the method further comprises calculating a decrease in the first amount of the at least one depletable chemical agent relative to an amount of another one or more components in the formulation based on the identified decrease in the first amount of the at least one depletable chemical agent.

124. The method of any one of claims 106-123, further comprising sampling an aliquot of the liquid formulation for analysis.

125. The method of claim 124, wherein the sampling is performed as needed and/or at predetermined time intervals and/or after a predetermined number of print cycles.

126. The method of any one of claims 106 to 125, wherein the reduction of the first amount of the depletable chemical agent is relative to an amount of another component or components contained within the formulation.

127. The method of any one of claims 106 to 126, wherein the reduction of the first amount of the depletable chemical is due to an undesired side reaction of the depletable chemical.

128. The method of claim 127, wherein the undesirable side reaction of the depletable chemical agent results in the formation of an undesirable byproduct within the liquid formulation.

129. The method of claim 128, wherein the method further comprises detecting the formation and optionally measuring/determining the amount of said undesired by-products in said liquid formulation.

130. The method of claim 129, wherein the method further comprises correlating the detected formation of the undesired byproduct with the reduction in the first amount of the depletable chemical.

131. The method of any one of claims 106 to 130, wherein the reduction of the first amount of the depletable chemical is due to contamination of the liquid formulation with at least one contaminant, and wherein formation of at least one undesirable byproduct is due to interaction between the at least one depletable chemical and the at least one contaminant.

132. The method of any one of claims 106 to 131, wherein the reduction in the first amount of the depletable chemical is due to contamination of ink in the liquid formulation.

133. The method of claim 132, wherein the ink contamination is due to one or more of: ink spillage, ink splash and recovery processes for the treatment formulation.

134. The method of any one of claims 114 to 133 wherein the ink comprises at least one binder and at least one colorant, and wherein the reduction in the first amount of the depletable chemical is due to an undesired side reaction of the depletable chemical with the at least one binder.

135. The method of any one of claims 106-134, wherein the method further comprises protecting the liquid formulation from contamination.

136. The method of any one of claims 128 to 135, wherein the method further comprises removing the byproduct from the liquid formulation.

137. The method of any one of claims 106-136, wherein the method further comprises measuring a volume of the liquid formulation, wherein when the measured volume is below a predetermined minimum volume, the method further comprises refilling the liquid formulation with liquid formulation to be substantially equal to or above the predetermined minimum volume.

138. The method according to any one of claims 106 to 137, wherein the depletable chemical agent is a polymer agent containing an amine nitrogen atom in a plurality of functional groups, which need not be identical and can be combined.

139. The method of claim 138, wherein the polymer has a relatively high charge density.

140. The method of claim 138 or 139, wherein the molecular weight of the polymer is equal to or greater than 10,000 g/mole.

141. The method of any one of claims 106 to 140, wherein the depletable chemical agent is a polymeric agent having at least one of: (a) a positive charge density of at least 3meq/g of said agent and an average molecular weight of at least 5,000, (b) a positive charge density of at least 6meq/g of said agent and an average molecular weight of at least 1,000, (c) a nitrogen content of at least 1% by weight and an average molecular weight of at least 50,000, and (d) a nitrogen content of at least 18% by weight and an average molecular weight of at least 10,000.

142. The method according to any one of claims 106 to 141, wherein the depletable chemical agent is a polymer agent having a density of positive charges.

143. The method of claim 142, wherein the positive charge density is at least 0.5meq/g, at least 1meq/g, at least 2meq/g, at least 3meq/g, at least 4meq/g, at least 5meq/g,6meq/g, at least 7meq/g, at least 8meq/g, at least 9meq/g, at least 10meq/g, at least 11meq/g, at least 12meq/g, at least 13meq/g, at least 14meq/g, at least 15meq/g, at least 16meq/g, at least 17meq/g, at least 18meq/g, at least 19meq/g, or at least 20meq/g of the agent.

144. The method of any one of claims 106 to 143, wherein the depletable chemical agent is a polymeric agent having an average molecular weight of at least 500, at least 800, at least 1,000, at least 1,300, at least 1,700, at least 2,000, at least 2,500, at least 3,000, at least 3,500, at least 4,000, at least 4,500, at least 5,000, at least 10,000, at least 15,000, at least 20,000, at least 25,000, at least 50,000, at least 100,000, at least 150,000, at least 200,000, at least 250,000, at least 500,000, at least 750,000, at least 1,000,000, or at least 2,000,000.

145. The method of any one of claims 106 to 144, wherein the depletable chemical agent is a polymer agent having an average molecular weight of at least 2,000, at least 10,000, or at least 25,000.

146. The method of any one of claims 106 to 145, wherein the depletable chemical agent comprises one or more nitrogen atoms that can be positively charged.

147. The method of claim 146, wherein the one or more nitrogen atoms constitute at least 1, at least 1.4, at least 2, at least 5, at least 8, at least 10, at least 15, at least 18, at least 20, at least 24, at least 30, at least 35, at least 40, at least 45, or at least 50 weight percent of the depletable chemical agent.

148. The method of any one of claims 106 to 147,wherein the depletable chemical is a composition comprising poly (diallyldimethylammonium chloride)A polymeric agent of units.

149. The method of any one of claims 106 to 147, wherein the depletable chemical agent is a composition comprising polyallylamineA polymeric agent of units.

150. The method of any one of claims 106 to 147, wherein the depletable chemical agent is a composition comprising poly (4-vinylpyridine)A polymeric agent of units.

151. The method of any one of claims 106-147, wherein the depletable chemical polymer agent is selected from the group consisting of: linear polyethylenimine, branched polyethylenimine, modified polyethylenimine, poly (diallyldimethylammonium chloride), poly (4-vinylpyridine), polyallylamine, vinylpyrrolidone-dimethylaminopropylmethacrylamide copolymer (Viviprint 131), vinylcaprolactam-dimethylaminopropylmethacrylamide hydroxyethyl methacrylate copolymer (Viviprint 200), vinylpyrrolidone and quaternized copolymer of dimethylaminoethyl methacrylate with diethyl sulfate (Viviprint 650), guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride.

152. The method of claim 151, wherein the depletable chemical polymer agent is Polyethyleneimine (PEI).

153. The method of any one of claims 106 to 152 wherein the first amount of the depletable chemical polymer agent in the formulation in the liquid receptacle is equal to or less than about 5, 4,3, 2, 1, 0.5, 0.4, 0.3, 0.2, 0.1, or equal to or at least about 0.05, or sometimes at least about 0.01 weight percent.

154. The method of any one of claims 106-153, wherein the depletable chemical polymer agent is a polymer agent that is PEI and wherein the predetermined threshold is at least 0.01 wt%, at least 0.05 wt%, at least 0.10 wt%, at least 0.15 wt%, or at least 0.20 wt%.

155. The method of any one of claims 106-154, wherein the depletable chemical agent is a polymeric agent that is PEI, and wherein the first amount thereof by weight in the liquid formulation is at most 6%, at most 5%, at most 4%, at most 3%, at most 2.5%, at most 2.0%.

156. The method of any one of claims 106 to 155, wherein the depletable chemical is a polymeric agent that is PEI, and wherein the first amount thereof by weight in the liquid formulation is in the range of 0.01 to 1%, 0.01 to 0.8%, 0.01 to 0.7%, 0.01 to 0.6%, 0.01 to 0.5%, 0.2 to 0.7%, 0.2 to 0.6%, or 0.2 to 0.5%.

157. The method of any one of claims 106 to 156, wherein said at least one depletable chemical is PEI wherein the first amount thereof in the formulation in liquid reservoir is 0.25 wt% and the second amount thereof in the replenishment reservoir is 25 wt% in water.

158. The method of claim 157, wherein when said first amount of said PEI in said liquid formulation is reduced below a predetermined threshold of 0.01 wt%, adding a portion of said second amount of said PEI to said liquid formulation, thereby supplementing the amount of said PEI in said liquid formulation to a value equal to or above said predetermined threshold (0.01 wt%), or supplementing the amount of said PEI in said liquid formulation to a value equal to said first amount (0.25 wt%).

159. The method of any one of claims 106 to 158, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein its average molecular weight is at least 20,000, at least 50,000, at least 100,000, at least 200,000, at least 350,000, at least 500,000, at least 700,000, at least 750,000, and optionally at most 3,000,000, at most 2,500,000, or at most 2,000,000.

160. The method of any one of claims 106-159, wherein the depletable chemical agent is a polymeric agent that is PEI, and wherein the PEI is a surfactant, a wetting agent, an anchoring agent, or any combination thereof.

161. The method of any one of claims 106 to 160, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the charge density of the PEI polymer is in the range of 16-20meq/g material.

162. The method of any one of claims 106 to 160, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the charge density of the PEI polymer is 8 meq/g.

163. The method of any one of claims 106 to 162, wherein the depletable chemical is silicone-functionalized PEI.

164. The method of any one of claims 106 to 163, wherein the depletable chemical agent is a quaternary ammonium compound.

165. The method of claim 164 wherein the quaternary ammonium compound is Larostat264A (BASF).

166. The method of claim 164, wherein the quaternary ammonium compound is Foamquat SAQ (linoleamidopropyl ethyl dimethyl ammonium ethyl sulfate 90).

167. The method of any one of claims 106 to 166, wherein the depletable chemical agent is water dispersible.

168. The method of any one of claims 106 to 166, wherein the depletable chemical agent is water soluble.

169. The method of any one of claims 106 to 168, wherein the depletable chemical is a solid at room temperature.

170. The method of any one of claims 134 to 169, wherein the at least one binder in the ink formulation is a negatively charged organic polymer resin.

171. The method of claim 170, wherein the negatively charged organic polymer resin has an average molecular weight of at least 8,000.

172. The method of claim 170 or 171, wherein the at least one binder in the ink formulation is an acrylic polymer and/or an acrylic-styrene copolymer.

173. The method of claim 170, wherein the binder is Joncryl 538 BASF.

174. The method of any one of claims 106 to 173, wherein the depletable chemical agent is PEI, and wherein the reduction in the first amount of PEI is due to an undesired side reaction thereof with the at least one binder.

175. The method of any one of claims 106 to 174, wherein the method further comprises detecting and/or measuring and/or calculating the concentration of the depletable chemical agent in the liquid formulation and calculating therefrom the reduction in the first amount of the depletable chemical agent.

176. The method of claim 175, wherein the depletable chemical agent is PEI and wherein the detecting and/or measuring and/or calculating is by spectroscopic means using the reaction of copper with the PEI.

177. The method of any one of claims 106 to 176, wherein the treatment formulation comprises:

at least one water-soluble polymer;

an aqueous carrier liquid; and

optionally, one or more of the following: (a) at least one humectant; (b) at least one surfactant and (c) at least one wetting agent.

178. The method of claim 177, wherein the treatment formulation further comprises at least one wetting agent.

179. The method of claim 178, wherein the wetting agent is PEI.

180. The method according to claim 177, wherein the water-soluble polymer is at least one modified polysaccharide.

181. The method of claim 180, wherein the modified polysaccharide is selected from a cellulose derivative, a cellulose ether, a methylcellulose, a hydroxypropyl methylcellulose, or any combination thereof.

182. The method of claim 181, wherein the modified polysaccharide is hydroxypropyl methylcellulose.

183. The method of any one of claims 1 to 182, wherein the treatment formulation is as disclosed and exemplified herein.

Technical Field

The present disclosure relates to systems and methods for preventing or minimizing printing defects.

Background

References considered to be relevant as background to the presently disclosed subject matter are listed below:

[1] piotr Warszynski et al, "Characteristics of polymeric multilayers" Effect of PEI and posttreatment after disposition "Journal of Colloid and Interface Science, Vol.305, No. 1/1 of 2007, p.46-56.

The following patent applications/publications by the applicant provide potentially relevant background information and are incorporated herein by reference in their entirety:

[2] WO 2017/208246 (published PCT/IL2017/050616, filed on 6/1/2017);

[3] WO 2019/111223 (published PCT/IB2018/059761, filed on 7.12.2018);

[4] WO 2015/036812 (published PCT/IB2013/002571, filed on 12.9.2013);

[5] WO 2015/036865 (published PCT/IB2014/002395, filed on 9, 11, 2014);

[6] WO 2013/132439 (published PCT/IB2013/051755, filed on 3, 5.2013);

[7] WO 2013/132418 (published PCT/IB2013/051716, filed on 3, 5.2013);

[8] WO 2013/132345 (published PCT/IB2013/000840, filed on 3/5/2013);

[9] WO 2013/132339 (published PCT/IB2013/000757, filed on 3/5/2013);

[10] WO 2017/208152 (published PCT/IB2017/053177, filed on 30/5/2017);

[11] WO 2019/012456 (published PCT/IB2018/055126, filed on 11/7/2018);

[12] WO 2020/003088 (publication filed 24/6/2019);

[13] U.S. patent No. 9,914,316;

[14] U.S. patent No. 9,186,884;

[15] WO 2013/132424 (published PCT/IB2013/051727, filed on 3, 5.2013);

[16] U.S. patent application publication 2015/0054865; and

[17] united states provisional application No.62/787,984, united states provisional application No. 62/790,890, united states provisional application No.62,825,568 and corresponding international application No. PCT/IB 2020/050001).

The admission of the above references herein should not be construed as implying any relationship between these and the patentability of the presently disclosed subject matter.

Disclosure of Invention

The inventors of the present invention have developed a system and method for preventing and/or minimizing printing defects associated with the undesirable depletion of at least one component used in a printing process. This component was found to be very important for the quality of the printed image and its depletion severely affected the quality of the printed image.

In particular, the inventors of the present invention have utilized a system for a printing process, such as an indirect printing process, in which the release surface of an Intermediate Transfer Member (ITM) is pretreated (e.g., coated) with a treatment formulation (e.g., an aqueous treatment formulation) prior to depositing an ink image on the release surface of the ITM. Applying a treatment formulation onto a surface of the ITM to form a thin wet treatment layer thereon, which is subjected to a drying process on the ITM release surface, thereby leaving a thin, substantially dry treatment film on the ITM release surface. Aqueous ink droplets comprising at least one organic polymer resin and at least one colorant in an aqueous carrier are then deposited (e.g., by inkjet deposition) onto the thin, substantially dry handling film to form an ink image thereon. The formed ink image is then subjected to a drying process to leave a substantially dry ink image residue on the substantially dry handling film. The substantially dry ink image is then transferred from the ITM surface to a final printed substrate (e.g., an aluminum foil-based, paper-based, or plastic-based substrate) along with a thin substantially dry handling film.

Examples of such printing processes and systems are disclosed in the applicant's aforementioned patent applications/publications (e.g. WO 2013/132418 and WO 2017/208152), the contents of which are incorporated herein by reference.

During the printing process, refilling of the ink and treatment formulations is required due to the consumption of the ink and treatment formulations used for printing purposes during the printing process.

The inventors of the present invention have found that the quality of the ink image produced in the above printing process may be degraded as the printing process proceeds. Sometimes the quality of the printed image may decrease at various stages of the printing process, sometimes even very early in the printing process, which means that the decrease in print quality may be independent of the number of execution of the printing cycle.

Furthermore, the inventors of the present invention have surprisingly found that the reduction in quality of the printed image, which may sometimes be reflected in the graininess of the image, is largely dependent on the presence of at least one ingredient in the treatment formulation. The inventors have found that without the components, the quality of the printed image is very low.

The inventors have further found that the reduction in print quality may be independent of the physical characteristics of the treatment formulation (such as viscosity and surface tension) and also independent of the age (freshness) of the treatment formulation or its temperature.

Furthermore, the inventors of the present invention have surprisingly found that sometimes the amount of treatment formulation required for such refilling exceeds the amount that would be expected based on the calculated amount of treatment formulation per printed substrate.

The inventors of the present invention have surprisingly found that components which are important for the image print quality (and thus for the performance of the printing process) may be depleted during the printing process or even when no active printing is performed. It is noted that the depletion of the ingredient is not due to its consumption for printing purposes during printing, but is the result of an undesired reaction with contaminants that inadvertently reach the reservoir holding the formulation containing the ingredient (e.g., the treatment formulation). In particular, the contaminants may originate from the ink formulation used in the printing process. The inventors have found that contamination has a significant negative impact on the quality of formulations containing the above ingredients.

The above-mentioned specific ingredients that are important to the image print quality and in which their depletion negatively affects the print quality are referred to herein as "exhaustible chemicals" or any linguistic variation thereof, such as "exhausted chemicals", "chemical exhaustible agents", and the like.

To avoid and/or prevent or minimize degradation of printed image quality, the inventors have developed novel systems and processes detailed herein.

In particular, the inventors have found that in order to counteract the print quality degradation associated with insufficient quality of the treatment formulation used in the indirect printing process, it is not necessary to replenish the entire treatment formulation (which includes all the ingredients of the carrier). The performance of the treatment formulation can be restored by simply adding exhausted chemicals to the treatment formulation. This provides advantages in terms of reduced cost and reduced waste, making the disclosed system and process more environmentally friendly.

The system and method of the present invention also advantageously ensure the stability of print quality.

Accordingly, the present invention provides, in one of its aspects, a system for printing, the system comprising:

a liquid reservoir configured to hold a formulation comprising a first amount (e.g., weight, volume, concentration) of at least one depletable chemical (in a liquid carrier, e.g., an aqueous liquid carrier) that is substantially equal to or greater than a predetermined threshold, wherein the formulation optionally further comprises at least one further component;

a replenishment reservoir configured to hold a second amount (e.g., weight, volume, concentration) of the at least one depletable chemical agent, optionally in at least one liquid carrier (e.g., the same or a different aqueous carrier than the liquid carrier of the formulation contained in the liquid reservoir);

The present invention provides, in another of its aspects, a method for preventing or minimizing print defects in a printing process, wherein the print defects are associated with a reduction in a first amount of at least one depletable chemical contained within a liquid formulation (optionally in a liquid carrier), the method comprising:

after identifying/detecting the reduction, adding a second amount of at least a portion of the at least one exhaustible chemical agent to the formulation, wherein the second amount of the at least a portion is sufficient to re-establish the first amount of the exhaustible chemical agent in the liquid formulation to be substantially equal to or greater than the predetermined threshold and/or wherein the second amount of the at least a portion is sufficient to counteract the reduction of the first amount relative to the amount of at least another component in the formulation, thereby preventing or minimizing the print defect.

In another of its aspects, the present invention provides a method for preventing or minimizing printing defects in a printing process, which utilizes the system described herein.

However, a further aspect of the invention in its aspects provides a system and process as described herein.

Brief Description of Drawings

In order to better understand the subject matter disclosed herein and to illustrate how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

fig. 1A shows a schematic diagram of a system (e.g., an apparatus) according to some embodiments of the invention.

Fig. 1B is a schematic side view of a printing system (e.g., a digital printing system) according to some embodiments of the invention.

Fig. 2 shows a graph depicting the results of measurements of the change in average viscosity of treatment formulations over time, according to some embodiments of the present invention.

Fig. 3 shows a graph depicting the results of measurements of the change in average surface tension over time for treatment formulations according to some embodiments of the present invention.

Fig. 4A-4C show a portion of a printed image (enlarged portion) obtained with a treatment formulation in an indirect printing process, the formulation being at different temperatures and different aging times, according to some embodiments of the present invention.

Fig. 5A-5B show printed images obtained during an indirect printing process according to some embodiments of the present invention using fresh treatment formulations that have not been used previously (fig. 5A) and treatment formulations that have been used for multiple printing cycles during the printing process (fig. 5B).

Fig. 6A-6D show printed images and their corresponding enlarged (magnified) portions obtained by combining fresh (unused) Treatment Formulation (TF) and used TF with fresh and used (aged) blanket (ITM) in an indirect printing process according to some embodiments of the present invention.

Fig. 7 shows a graph depicting the effect of aging (time) and temperature of a treatment formulation on graining of a printed image produced in an indirect printing process according to some embodiments of the present invention.

Fig. 8 shows a graph depicting the effect of ink contamination in a treatment formulation (at room temperature, RT) on graining of a printed image produced during indirect printing according to some embodiments of the present invention.

Fig. 9 shows a graph depicting the effect of the presence of ink contamination in a treatment formulation (at 50 ℃) on the graining of a printed image produced during indirect printing according to some embodiments of the present invention.

Fig. 10A-10D show printed images obtained using fresh TF, ink contaminated TF (with different ages and temperatures), and filtered treatment formulations in an indirect printing process according to some embodiments of the present invention.

Figures 11A-11B show images (Zygo x50) of polyethylene terephthalate (PET) slides coated with treatment formulations containing Polyethyleneimine (PEI) (figure 11A) and no PEI (figure 11B) according to some embodiments of the present invention.

Figure 12 illustrates the phase separation and precipitation observed in a glass tube after the ink binder was added to the PEI solution.

Fig. 13A-13D show images of PET slides (left side of the figure) coated with: PEI containing treatment formulation (fig. 13A), PEI free treatment formulation (fig. 13B), TF stored for 3 days and at 50 ℃ contaminated with ink (fig. 13C), and TF contaminated with ink but containing an additional repair amount of PEI (fig. 13D). Fig. 13A-13D further show corresponding printed images (magnified) obtained during indirect printing using corresponding treatment formulations according to some embodiments of the present invention (right side of figure).

Fig. 14A-14B show graphs depicting graining of printed images produced during indirect printing with fresh TF, ink contaminated TF and ink contaminated TF with an added (repaired) amount of PEI (fig. 14A). Fig. 14B shows an enlarged portion of a corresponding printed image obtained during indirect printing using a corresponding treatment formulation, according to some embodiments of the invention.

Fig. 15A-15C show (upper part) printed images generated during indirect printing using fresh TF (fig. 15A), ink contaminated TF (fig. 15B) and ink contaminated TF with added (repaired) amount of PEI (fig. 15C). Fig. 15A-15C further show (lower portion) enlarged portions of respective printed images according to some embodiments of the present invention.

Figure 16 shows a scheme illustrating the detection of PEI by the addition of copper ions to a PEI solution, which results in blue emission from the solution and strong absorption at about 275nm (with lower absorption at about 650 nm).

Figures 17A-17L illustrate the color reaction observed after titration with copper of various fresh TFs with different PEI concentrations (the corresponding observed particle size values are numbers detailed in the upper part of these figures).

Fig. 18 shows the absorption spectra observed after the addition of copper to various TFs with different PEI concentrations according to some embodiments of the present invention.

FIG. 19 shows a calibration curve at 285nm generated with treatment formulations having known PEI concentrations in the presence of copper according to some embodiments of the present invention.

Figure 20 shows PEI concentrations for various TFs according to some embodiments of the invention calculated at two different dilutions based on the calibration curve of figure 19.

Figure 21 shows PEI concentrations for various TFs according to some embodiments of the invention calculated in the presence and absence of copper (the latter used as a control test) based on the calibration curve of figure 19.

Figure 22 shows a correlation between particle size of a printed image and PEI concentration in the TF used to generate the image according to some embodiments of the present invention.

Detailed Description

The present invention is based on a new concept of ensuring the quality of the printed image obtained during printing by supplementing the specific components used during printing.

Accordingly, the present invention provides, in one of its aspects, a system for printing, the system comprising:

a replenishment reservoir configured to hold a second amount of the at least one depletable chemical, optionally in at least one liquid carrier;

a detection tool configured to identify at least: (i) whether the first amount of the depletable chemical agent decreases below a predetermined threshold and/or (ii) a functional capacity of the at least one depletable chemical agent decreases;

Various embodiments will be described in detail herein in connection with the above-mentioned aspects. It is noted that one or more embodiments detailed in connection with the system of the invention may also be applied to the method of the invention, mutatis mutandis, and vice versa.

In some embodiments, the first and second amounts of the depletable chemical in the liquid reservoir and the replenishment reservoir are provided in% w/w (e.g., grams of depletable chemical per 100 grams of formulation/solution containing the depletable chemical), respectively.

Unless otherwise indicated, the term "concentration" refers to w/w-, i.e., the proportion by weight of a certain component of a formulation/solution/dispersion (e.g., treatment formulation, printing liquid such as an ink formulation, etc.) relative to the total weight of the formulation/solution/dispersion. Sometimes, the concentration is provided in w/w% (which may be interchanged with% w/w or wt%), i.e., the weight of a component of a formulation/solution/dispersion (e.g., treatment formulation, printing liquid such as ink formulation, etc.) that contains that component per 100 grams of that formulation/solution/dispersion.

The system and method of the present invention are directed to improving print quality by counteracting effects associated with the depletion of at least one depletable chemical whose presence during the printing process is significant to both the performance of the printing process and the quality of the resulting printed image. Unless otherwise indicated, depletion of the depletable chemical agent may be reflected in one or more of the following "reduction" situations that the systems and methods of the present invention are intended to counteract:

-the first amount of the depletable chemical agent is reduced below a predetermined threshold;

-a reduction in the functional capacity of at least one depletable chemical agent; and

-the first amount of the depletable chemical agent is reduced relative to the amount of at least another component of the formulation.

In some embodiments, the depletion of the depletable chemical may be reflected in a decrease in the first amount of the depletable chemical below a predetermined threshold.

In some embodiments, the depletion of the depletable chemical agent may be reflected in a reduction in the functional capacity of the at least one depletable chemical agent.

In some embodiments, the depletion of the depletable chemical agent may be reflected in a decrease in the first amount of the depletable chemical agent relative to the amount of at least another component in the formulation.

The following disclosure further details the reduction detailed above.

Thus, the at least one depletable chemical agent is present in the formulation in a first amount that is substantially equal to or greater than a predetermined threshold.

The term "predetermined threshold" is used herein in connection with an amount of at least one depletable chemical agent of a formulation (which is contained in a liquid reservoir), which is equal to or less than a first amount, and represents a substantially different value (i.e., a different integer ± standard deviation) predetermined based on a reference formulation having a quality that meets one or more of the stability, functionality, and compatibility (e.g., compatibility with a printing process that utilizes the formulation) of the formulation. These qualities may be directly related to the quality of the image produced with the formulation during printing.

As used herein, "and/or (and/or)" is to be taken as defining one or the other or both of the terms to which the phrase refers.

According to the invention, the exhausted chemical agent performs one or more functions that are critical, alone or in combination, to the performance of the formulation in the printing process, which performance may also be reflected in the image print quality. Thus, as used herein, the terms "functional capability," "functionality," or any linguistic variation thereof, used in reference to a depleting chemical agent, refer to the one or more functions.

Non-limiting examples of functions that a depletable chemical may have are affecting one or more of the following: solubility; wettability; viscosity; elasticity; adhesion; moisture absorption; density; porosity; and tensile strength.

A further non-limiting function of the exhausted chemical agent is to achieve one or more of the following features: good wettability of the surface of the ITM coated with a formulation comprising a depletable agent; the film formed on the ITM has good adhesion; improved ink image quality (which may be reflected in low particle size of the image); giving the ink good wetting and spreading properties on the coated ITM. To this end, in some embodiments, the exhausted chemical agent may serve as one or more of: wetting agents, surfactants and anchoring agents (the latter may be particularly useful for improving pinning of treatment formulations on ITMs and reducing coalescence of wet treatment coatings from ITMs).

In some embodiments, the functions that can be performed by the depleting chemical are one or more of surfactants, wetting agents, and anchoring agents.

In some embodiments, the function performed by the depletable chemical is to provide good wettability of the ITM surface coated with a treatment formulation comprising the depletable agent.

According to the invention utilized in the printing process, the functional capacity of the depletable agent can be directly related to its amount in the treatment formulation. Thus, at times, a reduction in the functional capacity of the at least one depletable chemical agent is directly related to a reduction in the first amount of the depletable chemical agent in the formulation below a predetermined threshold.

In some embodiments, for example, when utilized in an indirect printing process, the functional capacity of the at least one depletable chemical agent decreases and/or the first amount of the depletable chemical agent decreases below a predetermined threshold is directly related to print quality.

In some embodiments, the print quality may be reflected in the granularity of the printed image (the lower the granularity, the better the quality). For this reason, the depletable chemical may serve a function related to image particle size.

In some embodiments, the first amount of the depletable chemical may be substantially equal to or greater than the predetermined threshold mentioned above.

In some embodiments, the amount of the depletable chemical agent may be provided by weight, volume, or concentration.

In some embodiments, the replenishment reservoir is configured to hold only the at least one depletable chemical agent, optionally in at least one liquid carrier, i.e., the replenishment reservoir is absent other functional components of the formulation in the liquid formulation and replenishes only the depletable chemical agent.

In some embodiments, the at least one depletable chemical agent is present in the replenishment reservoir in liquid form (e.g., optionally as a solution or dispersion in the same or a different liquid carrier as is present in the liquid reservoir).

In some embodiments, the replenishment reservoir and the liquid reservoir may be in liquid communication (e.g., via a fluid conduit), thereby allowing (e.g., upon identifying a decrease in the first amount of the depletable chemical below a predetermined threshold or a decrease in the functional capacity of the at least one depletable chemical) a quantity (e.g., at least a portion of the second amount) of the at least one depletable chemical to be transferred from the replenishment reservoir to the liquid reservoir.

In some embodiments, the transfer means may further comprise a conditioning means configured to condition the amount of transfer of the depletable chemical from the replenishment reservoir to the liquid reservoir and/or to avoid reverse flow of liquid from the liquid reservoir to the replenishment reservoir.

In some embodiments, the system of the present invention may further comprise means (regulatory means) for preventing reverse flow of liquid from the liquid reservoir to the refill reservoir (e.g., for preventing contamination, such as ink contamination that may be caused by ink seeping into the liquid reservoir). In some embodiments, the tool includes at least one safety valve that allows one-way flow of liquid from the refill reservoir to the liquid reservoir. For example, a closure valve may be inserted between the liquid reservoir and the refill reservoir and when the closure valve is open, it allows the refill fluid to be transferred from the refill reservoir to the liquid reservoir. In some embodiments, the system of the present invention may further comprise means for operating the valve to an open state, and means for closing the valve upon completion of replenishment, for example when the amount of the at least one depletable chemical agent in the liquid reservoir reaches (after said transfer) a value equal to or greater than the aforementioned predetermined threshold value.

In some embodiments, replenishment completion may be considered when the amount of the at least one depletable chemical in the liquid reservoir reaches (after the transfer) a value below the first amount but above a detection/measurement value below a predetermined threshold.

In some embodiments, the second amount (e.g., wt%) of the at least one depletable chemical in the replenishment reservoir may be greater than the first amount (e.g., wt%) of the at least one depletable chemical in the liquid reservoir, and after transfer, dilution of the transferred portion of the depletable chemical may occur in the liquid reservoir.

The methods and systems of the present invention may involve mixing at least one depletable chemical, for example, to provide homogeneity. Thus, in some embodiments, the system may optionally further comprise a mixing means (e.g., in one or more of the liquid reservoir and the replenishment reservoir) configured to mix (and/or uniformly disperse) the at least one depletable chemical agent in the liquid reservoir and/or the replenishment reservoir. To this end, the process of the invention may further comprise a corresponding mixing.

The system of the present invention comprises a transfer means configured to transfer at least a portion of the second amount of the at least one depletable chemical from the replenishment reservoir to the liquid reservoir. In some embodiments, the system may further comprise a metering pump for pumping a controlled amount of the depletable chemical from the replenishment reservoir into the liquid reservoir, and optionally a mixing means, such as a mixing device, for mixing the displaced amounts in the liquid reservoir.

In some embodiments according to the invention, the transfer may be effected manually, for example by a system operator.

In some embodiments, the amount of the depletable chemical (present in the replenishment reservoir) added may be provided in solid form. To this end, the depletable chemical agent is present in solid form in the replenishment reservoir, and the system may optionally further comprise means for mixing, dissolving (e.g., solubilizing) or dispersing the solid depletable chemical agent in, for example, at least one liquid carrier (which may be the same as or different from the liquid carrier of the formulation contained in the liquid reservoir). To this end, the methods of the present invention may further mix, dissolve (e.g., solubilize), or disperse the depletable chemical agent present in the refill reservoir.

In some embodiments, the method may further comprise mixing at least a portion of the second amount of the at least one depletable chemical agent in the liquid formulation.

In some embodiments, the methods and systems may involve heating to help solubilize the solid depletable agent. To this end, the system of the present invention may further comprise a heating means configured to assist in solubilizing the solid depletable chemical agent. To this end, the method of the present invention may further include corresponding heating (to help solubilize the solid-exhaustible chemical agent).

In some embodiments, the systems and methods of the present invention are used for indirect printing.

In some embodiments, the system of the present invention may further comprise at least one printing liquid reservoir (e.g., a printing bar) configured to hold a printing liquid, wherein the printing liquid is optionally an ink, further optionally a water-based ink (e.g., an aqueous ink formulation).

In some embodiments, the system may further comprise an intermediate transfer unit (ITM).

In the methods and systems of the invention, in some embodiments, the formulation in the liquid reservoir is a treatment formulation configured for application to and formation of a coating (e.g., substantially as described herein) on at least a region of the release surface of the ITM.

In some embodiments, the formulation is applied to the release surface prior to applying the printing liquid (e.g., aqueous ink formulation) to the release surface.

As used herein, the term "treatment formulation" means that the formulation is used with the ITM of a printing system for the purpose of treating the release surface of the ITM with the formulation. The treatment formulation may also be used to cool and/or clean the release surface of the ITM.

In some embodiments, the methods and systems of the present invention may utilize one or more detection tools (such as a detection unit) configured to, optionally, continuously identify the presence of a depletable chemical in a formulation (e.g., a treatment formulation) and measure and/or calculate its amount in the formulation and/or calculate its percentage relative to the formulation amount or relative to other components of the formulation. Non-limiting examples of such detection tools are spectroscopic tools [ e.g., visual (colorimetric), infrared), physical tools, conductivity measurement tools, pH measurement tools, refractive index measurement tools, density measurement tools, specific gravity measurement tools, or any combination thereof. The detected value (e.g., measured and/or calculated) may then be compared to a predetermined threshold and the amount of the exhaustible chemical may be replenished as needed.

In some embodiments, the detection tool is selected from the group consisting of a visual tool, a spectroscopic tool, a spectrophotometric tool, an electronic tool, a chemical tool, a physical tool, a print quality-based tool, or any combination thereof.

In some embodiments according to the invention, the detection means is configured to measure and/or calculate whether the first amount of the depletable chemical agent decreases below a predetermined threshold. To this end, the method of the invention may involve measuring and/or calculating the reduction.

In some embodiments according to the invention, the detection means is configured to detect/measure the amount of the at least one depletable chemical in the liquid reservoir, and the system is configured to calculate whether the first amount of the at least one depletable chemical decreases below a predetermined threshold based on the detected/measured amount. To this end, the method of the invention may involve detecting/measuring and/or calculating the reduction.

In some embodiments, the methods of the invention further comprise identifying whether the first amount of the at least one depletable chemical agent decreases below a predetermined threshold, wherein the identifying is accomplished by a detection tool selected from a visual tool, a spectroscopic tool, a spectrophotometric measuring tool, an electronic tool, a chemical tool, a physical tool, a print quality-based tool, or any combination thereof, and wherein the method further comprises calculating a decrease in the first amount of the at least one depletable chemical agent relative to the amount of another component or components in the formulation based on the identified decrease in the first amount of the at least one depletable chemical agent.

In some embodiments according to the invention, the detection means is configured to measure and/or calculate a decrease in the first amount of the depletable chemical relative to the amount of at least one further component in the formulation. To this end, the method of the invention may involve measuring and/or calculating the reduction.

In some embodiments according to the invention, the detection means is configured to measure and/or calculate a reduction in functional capacity of the at least one depletable chemical agent. To this end, the method of the invention may involve measuring and/or calculating the reduction.

In some embodiments, the system includes means for detecting, measuring, or calculating the concentration of the depletable chemical agent in the formulation contained within the liquid reservoir and calculating therefrom a decrease in the first amount of the depletable chemical agent.

In some embodiments, the method comprises detecting and/or measuring and/or calculating the concentration of the depletable chemical agent in the liquid formulation and calculating therefrom the decrease in said first amount of said depletable chemical agent.

In some embodiments according to the invention, the detection tool is configured to record and/or report (e.g., to a system operator) one or more of the aforementioned reductions.

In some embodiments according to the invention, the detection means is configured to activate the transfer means once one or more of the aforementioned reductions have been identified.

In some embodiments according to the invention, the system may further comprise a control unit configured to control replenishment of the at least one depletable chemical agent in the liquid reservoir and optionally configured to activate the transfer means once it has been identified that the first amount of said depletable chemical agent has decreased below a predetermined threshold and/or that the functional capacity of the at least one depletable chemical agent has decreased.

In some embodiments, the control may be automatic or semi-automatic (a combination of machine and manual operations).

In some embodiments, the transfer may be manual.

In some embodiments according to the invention, the system may further comprise communication means configured to transfer data/information between said detection means to said control unit.

In some embodiments according to the invention, the transfer tool may be one or more of a pressure-based tool, a jetting tool, a spraying tool, or a gravity tool. Other means known in the art may also be suitable. To this end, the present methods may further involve the use of other tools known in the art.

In some embodiments, the detection tool may be configured to specifically identify a reduction in the amount of the depletable chemical agent based on the chemical and/or physical characteristics of the depletable chemical agent as disclosed herein. To this end, the methods of the invention may involve quantifying the amount of the depletable chemical agent in the formulation based on the chemical and/or physical properties of the agent.

In some embodiments, the systems of the invention may further comprise a kit configured to quantify the amount of the depletable chemical agent in the formulation based on the chemical and/or physical properties of the agent.

In some embodiments, the depletable chemical comprises a nitrogen atom and the detection/measurement tool and/or kit is specific for detecting them.

In some embodiments, the depletable chemical is a nitrogenous agent (e.g., polyethyleneimine), and the detection unit comprises a spectroscopic tool (e.g., in the visible and/or infrared) configured to detect the nitrogenous agent based on the reaction of the copper cation/salt with the nitrogenous depletable chemical. To this end, the system of the invention may further comprise a kit configured to quantify the amount of the depletable chemical in the formulation, wherein the kit comprises a copper ion solution and instructions for use.

In some embodiments, the systems and methods of the present invention may further comprise sampling an aliquot from the liquid formulation for analysis (e.g., identifying/determining/measuring/calculating the amount of the at least one depletable chemical agent in the formulation). To this end, the system of the present invention may further comprise at least one sampling unit configured to take an aliquot of the formulation from the liquid reservoir for further analysis.

In some embodiments, sampling is performed as needed and/or at predetermined time intervals and/or after a predetermined number of print cycles.

In some embodiments, the sampling unit is configured to withdraw an aliquot of the formulation from the liquid reservoir as needed (e.g., when low print quality is observed and the amount to be replenished needs to be determined), and/or at predetermined time intervals and/or after a predetermined number of print cycles.

In some embodiments, the system of the present invention may further comprise means for detecting and/or measuring and/or calculating the concentration of the depletable chemical agent in the formulation contained in the liquid reservoir and calculating therefrom the decrease in the first amount of depletable chemical agent. To this end, the method of the present invention further comprises detecting and/or measuring and/or calculating the concentration of the depletable chemical agent and calculating therefrom a decrease in the first amount of the depletable chemical agent, e.g. whether it decreases below a predetermined threshold.

In some embodiments according to the invention, the reduction in the first amount of the depletable chemical may be relative to the amount of the other component or components of the formulation, i.e. the amount of the other component or components of the formulation remains unchanged, e.g. so that the relative concentration in the treatment formulation remains unchanged, but only the concentration of the depletable chemical is reduced. In other words, the depletable chemical agent is the only agent that is depleted, while the remaining components are maintained in a constant amount, such as weight percent, relative to each other.

In some embodiments, the system of the invention is configured to identify a decrease in the first amount of the at least one depletable chemical agent relative to the amount of the at least one other component in the formulation. In some embodiments, the system is configured to provide a signal indicative of a need to add the at least one depletable chemical to the liquid formulation to thereby reestablish the first amount of the depletable chemical in the liquid formulation substantially equal to or greater than the predetermined threshold and thereby counteract a reduction in the first amount of the at least one depletable chemical relative to the amount of at least one other component in the formulation. In this regard, the method of the invention comprises identifying a decrease in the first amount of the at least one depletable chemical relative to the amount of the at least another component in the formulation and adding a second amount of at least a portion of the at least one depletable chemical to the formulation to thereby reestablish the first amount of the depletable chemical in the liquid formulation substantially equal to or greater than a predetermined threshold and thereby counteract the decrease in the first amount of the at least one depletable chemical relative to the amount of the at least another component in the formulation. To this end, the method may further provide a signal indicative of a need to add the at least one depletable chemical agent to the liquid formulation.

In this regard, it should be noted that the depletion of the depletable chemical should be assumed to be one that is not due to depletion of the depletable chemical for the purposes of the printing process (e.g., depletion of the processing solution for the purposes of coating the ITM). The depletable chemical is consumed during the printing process, for example, in a controlled manner according to a predetermined program, along with other components of the formulation. Thus, the relative amount of the depletable chemical relative to the amount of the other components of the formulation will remain substantially constant during the printing process. Once depletion of the depleted chemical agent occurs (e.g., due to ink contamination), the relative amounts mentioned above will vary depending on the degree of depletion. The systems and methods of the present invention serve to offset such depletion by adding further amounts of depletable agents to repair their depletion and thereby minimize the negative effects (e.g., print quality degradation) associated with such depletion.

In some embodiments, in the methods and systems of the present invention, after identifying a decrease in the first amount of the depletable chemical below the aforementioned predetermined threshold, for example, a desired amount of at least one depletable chemical is added to the liquid formulation, for example, to reestablish the first amount of the depletable chemical in the liquid formulation or at least to increase the amount to be at or above the predetermined threshold. The addition may be provided in a predetermined spectrum referred to herein as a predetermined supplemental spectrum.

In some embodiments, the predetermined replenishment profile is selected to increase the amount of the depletable chemical agent to a value substantially equal to or greater than the aforementioned predetermined threshold, or sometimes to any other predetermined value below/above the predetermined threshold.

To this end, the system of the present invention may further comprise a control unit configured to control the replenishment of the at least one depletable chemical agent in the liquid reservoir according to the replenishment spectrum.

Referring now to fig. 1A, a schematic diagram of a system 100 (e.g., an apparatus) according to some embodiments of the invention is illustrated. The system includes a liquid reservoir 102 configured to hold a formulation comprising a first amount of at least one depletable chemical agent. The system further includes a refill reservoir 104 containing a quantity of at least one depletable agent. The system further includes a transfer unit 106 configured to transfer an amount of at least one depletable agent from the replenishment reservoir 104 into the liquid reservoir 102. The transfer unit 106 can further include a regulatory tool configured to regulate the amount of transfer and/or prevent reflux.

One example of such a transfer unit 106 is a fluid conduit that allows an amount of at least one depletable agent to be transferred from the replenishment reservoir 104 to the liquid reservoir 102. To this end, the system optionally further comprises a safety valve configured to prevent reverse flow of liquid from the liquid reservoir 102 to the replenishment reservoir 104.

In fig. 1A, the system 100 further includes a detection unit 108 configured to measure the amount and/or identify the depletion of at least one depletable chemical in the liquid reservoir 102.

The system may further include a sampling unit (not shown in fig. 1A) configured to withdraw an aliquot of the formulation in the liquid reservoir 102 for further analysis (e.g., to determine the amount of the at least one depletable chemical agent). Alternatively, the detection unit may measure and/or detect and/or identify depletion of the at least one depletable chemical agent in the reservoir.

The system optionally further includes a control unit 110 configured to control replenishment of the at least one depletable chemical in the liquid reservoir 102 by activating transfer of an amount of the depletable chemical from the replenishment reservoir 104 to the liquid reservoir 102.

The control unit 110 may control the replenishment as needed, e.g., based on feedback from the detection unit, and/or may periodically activate the replenishment based on a predetermined replenishment profile (e.g., replenish a predetermined amount of the depletable chemical once within a predetermined period of time).

In some embodiments, the system 100 in fig. 1A may further comprise one or more further units, e.g. as detailed herein.

In some embodiments, a system of the present invention, such as system 100 in fig. 1A, can form part of a printing system, such as described in detail herein (see, e.g., printing 10 system of fig. 1B).

In some embodiments, the system of the present invention may further comprise a processing utility.

In some embodiments, the processing utility may be configured to provide a signal indication to a user (e.g., a system operator) indicating a need to replenish the at least one depletable chemical agent in the liquid reservoir after identifying a decrease in the first amount of the depletable chemical agent below the aforementioned predetermined threshold and/or after identifying a decrease in the functional capability of the at least one depletable chemical agent (which may be reflected in the quality of the printed image).

In some embodiments, the signal indicator may be a visual signal, an audio signal, or a combination thereof.

In some embodiments, the replenishment may be performed by a user, e.g. according to a spectrum to be determined based on the printing conditions, optionally according to a predetermined replenishment spectrum, or may be performed automatically by the control unit, e.g. after approval by a system operator, e.g. by activating a controller (such as an on/off switch), e.g. according to a predetermined replenishment spectrum.

In some embodiments, the system may optionally further comprise means for stopping the printing process and resuming the printing process once replenishment is achieved/completed.

In some embodiments, the complementary spectrum may define one or more of: an amount (e.g., volume) of the at least one depletable chemical to be transferred from the replenishment reservoir to the liquid reservoir; the frequency of the supplement; the duration of the transfer; the manner of transfer (e.g., continuously or sequentially); the transfer rate.

In some embodiments, the complementary spectrum may be determined based on one or more of: a first amount and/or a second amount of a depletable chemical; the extent of said reduction; a detected decrease (e.g., an amount of depletable chemical remaining in the liquid reservoir after the decrease); the relative amount of the depletable chemical agent relative to the other component or components contained within the formulation.

In some embodiments, the complementary spectrum may be defined based on, for example, one or more of the following printing conditions, the nature of the print medium, the printing time/duration, the number of print cycles, the number of numbers or pages printed, one or more printing temperatures, the printing rate, the quality/lifetime of the formulation, the quality/lifetime of the ITM, the degree of contamination of the formulation by external contaminants (such as ink).

In some embodiments, the systems and methods of the present invention further comprise processing the image produced by the printing process and evaluating the image print quality thereof, wherein replenishment/addition of the depletable chemical agent in the liquid formulation is required when the image print quality is below a predetermined required quality (thus, performing the addition of at least a portion of the second amount of the at least one depletable chemical agent to the liquid formulation). To this end, the system of the invention utilizes a processing utility configured to process the image and evaluate the print quality thereof, wherein the control unit of the system is configured to control replenishment of the at least one depletable chemical agent in the liquid reservoir when the image print quality is below a predetermined required quality.

In some embodiments, the methods and systems of the present invention generate an output indicative of image quality, wherein replenishment/addition of the depletable chemical agent in the liquid formulation is required when the output is below a predetermined threshold parameter (thus, performing addition of at least a portion of the second amount of the at least one depletable chemical agent to the liquid formulation). To this end, the system of the present invention utilizes a processing utility configured to generate the output, and wherein when the output is below a predetermined threshold parameter, the control unit is configured to control or cause replenishment of the at least one depletable chemical agent in the liquid reservoir.

In some embodiments, the image print quality is determined based on the granularity of the image (the lower the granularity, the better the quality). To this end, the output reflects a value indicating the granularity of the image.

In some embodiments, the systems and methods of the present invention display the output on a visual display unit, an audio device, or a combination thereof. To this end, the system of the present invention may further include a display unit.

In some embodiments, the predetermined threshold parameter comprises a substantially different value or range of values indicative of a desired quality of the printed image (e.g., print quality may be determined based on one or more image pixels, the threshold parameter being a different value for one pixel, an average value for some pixels, or a range of values for various pixels).

In some embodiments, when the output is below a predetermined threshold (e.g., a predetermined threshold indicative of an image being defective), the system of the present invention is configured to provide an alert to the user and the method provides an alert to the user, and at times automatically aborts the printing process, and optionally resumes the printing process after completion of replenishment of the depletable chemical (in the liquid reservoir).

In some embodiments, the system of the present invention may further comprise a user interface. At times, a user interface may be used to allow a user to introduce one or more desired printing conditions for a printing process into the processing utility.

In some embodiments, the system of the present invention may further comprise a memory comprising a database of one or more image quality predetermined threshold parameters of the printing process.

In some embodiments, the processing utility is configured to associate a predetermined threshold parameter of image quality from the database with the output generated during the printing process.

In some embodiments, the system of the present invention may further comprise means for recording a replenishment history. To this end, the system may be configured to record the replenishment occurrence and optionally store it in memory. The system may further be configured to determine the quality of the treatment formulation based on the latter, and in case a predetermined amount of replenishment cycles and/or an amount of exhaustible chemical is replenished and/or an amount of exhaustible chemical in the replenishment reservoir is consumed, stop the printing process and/or provide an indication to the user about the history of replenishment, optionally followed by a decision (or automatic/semi-automatic) by the user whether to proceed with further replenishment or to discard the formulation in the liquid reservoir (when its quality is insufficient, e.g. due to a large number of replenishment cycles exceeding the predetermined number of replenishment cycles) and fill it with a new (fresh) formulation.

In some embodiments, the reduction in the first amount of the depletable chemical or the reduction in the functional capacity of at least one depletable chemical may be due to an undesired side reaction of the depletable chemical.

In some embodiments, undesirable side reactions of the exhaustible chemical agent result in the formation of undesirable by-products.

As used herein, the term "undesirable byproducts" refers to byproducts produced following reaction of at least one ingredient that does not form part of the treatment formulation or that does not achieve any functionality of the treatment formulation with the exhaustible chemical, which byproducts are not functional in the formulation, e.g., in the treatment formulation and/or during printing.

In some embodiments, the systems and methods of the present invention may further comprise detecting the formation of undesired by-products and optionally measuring the amount thereof. To this end, the system of the present invention may further comprise means for detecting the formation of undesired by-products in the liquid reservoir and for measuring/determining/calculating the amount of said by-products in the liquid reservoir.

In some embodiments, the methods and systems of the present invention may further comprise correlating the detected formation of the undesired byproduct with a reduction in the first amount of the depletable chemical. To this end, the system of the present invention may further comprise means configured to correlate the detected formation of the undesired by-product with a reduction in the first amount of the depletable chemical agent. In some embodiments, the system may further include a means configured to calculate a reduction in the first amount of the depletable chemical from an amount of an undesired by-product in the liquid reservoir.

In some embodiments, the reduction in the first amount of the depletable chemical may be due to contamination of the formulation (in the liquid reservoir) with at least one contaminant and formation of at least one undesirable byproduct due to an interaction between the at least one depletable chemical and the at least one contaminant, which may be a reversible interaction or an irreversible interaction.

In some embodiments, the methods and systems of the present invention are used for printing. To this end, the system further includes at least one printing liquid reservoir (e.g., an ink reservoir) configured to hold a printing liquid (e.g., and an ink formulation), and wherein the reduction in the first amount of the depletable chemical is due to printing liquid contamination (e.g., ink contamination) in the liquid reservoir holding the treatment formulation according to the invention (e.g., entry of an ink component into the liquid reservoir holding the treatment formulation containing the depletable chemical).

In some embodiments, the systems of the present invention may further comprise means for removing ink image residue or treatment formulation residue from the release layer surface of the ITM and recovering the treatment formulation residue (into the liquid reservoir). To this end, the system of the present invention may further comprise one or more of the following:

(i) a mechanical residue removal mechanism adapted to mechanically remove ink image residues or treatment formulation residues from the release layer surface;

(ii) a doctor blade mechanism adapted to mechanically remove ink image residue or treatment formulation residue from a surface of the release layer; and

(iii) a washing station for removing ink image residues or treatment formulation residues from the surface of the release layer,

wherein the system optionally further comprises means for recycling the treatment formulation residue to the liquid reservoir.

In some embodiments, the ink contamination results from the recycling of process formulation residues.

In some embodiments, ink contamination may be due to one or more of the following: ink overflow; ink splash (e.g., from ink ejection nozzles); insufficient removal of ink image residue; ink residue is present in the recovered treatment formulation residue (e.g., due to insufficient transfer of ink from the ITM to the final substrate).

In some embodiments, ink contamination may be due to one or more of ink spillage, ink splashing, and process formulation recovery.

In some embodiments, ink contamination may be due to the recycling process of the treatment formulation.

Sometimes, ink contamination may increase as print cycles increase due to the accumulation of undesirable ink contamination.

In some embodiments, the printing liquid is an ink (e.g., an ink formulation) comprising at least one binder (e.g., a negatively charged organic polymeric resin) and at least one colorant (e.g., the colorant is comprised of a pigment), and wherein the reduction in the first amount of the depletable chemical or the reduction in the functional capacity of the at least one depletable chemical is due to the formation of undesirable byproducts (in a liquid receptacle housing a treatment formulation according to the present invention) by the depletable chemical undergoing an undesirable side reaction with the at least one binder.

In some embodiments, in a system according to the present invention, the refill reservoirs are located far enough (sufficiently spaced) from at least one ink reservoir (e.g., a print bar) to avoid the effects of ink contamination of the refill reservoirs (e.g., due to ink splash/overflow).

In some embodiments, the system of the present invention may further comprise a protection unit configured to protect the liquid reservoir (containing the treatment formulation of the present invention) from contamination, such as ink contamination. To this end, the method of the invention further comprises protecting the liquid formulation from contamination.

In some embodiments, the protective unit can utilize a selective filter, for example, a selective filter that chemically interacts with one or more ink components (e.g., a binder) to selectively capture the one or more ink components. The protection unit may be positioned downstream of or in close proximity to the liquid reservoir opening or at the liquid reservoir opening. To this end, the system may further comprise connection means configured to connect the protection unit with the liquid receptacle. The system may further protect the refill reservoir with the protection unit.

In some embodiments, the methods and systems of the present invention may further comprise removing undesired by-products. To this end, the system of the present invention may further comprise a tool configured to remove the byproduct from the liquid reservoir (e.g., once the byproduct is formed and/or once the byproduct is detected). Such tools may enable the treatment formulation to further function and optionally avoid undesirable side effects associated with the by-products, such as clogging one or more system components/units.

Non-limiting examples of tools to remove undesired byproducts are one or more of the following: filtration, for example, wherein the by-product is a solid or semi-solid that can be physically filtered from the liquid treatment formulation; phase separation, for example, where the by-product forms a distinct phase (such as forming a gel that is a separate phase from the liquid formulation); recycling, optionally followed by decanting the liquid component (solution) and discarding the by-product, e.g., in the case where the by-product is a solid product, and recycling the liquid component to the liquid reservoir.

In some embodiments, the methods and systems of the present invention further comprise measuring the volume of the liquid formulation (in the liquid reservoir), wherein when the measured volume is below a predetermined minimum volume, the printing process is stopped and the liquid formulation is refilled with an additional volume of the liquid formulation to achieve a volume substantially equal to or above the predetermined minimum volume. To this end, the system of the present invention may further comprise a measuring means configured to measure the volume of liquid in said liquid reservoir, and the system (e.g. the control unit or the processing unit) is configured to instruct the user to refill the liquid reservoir with a new liquid formulation. Similarly, the system of the present invention may further comprise a measuring means configured to measure the amount (e.g. volume/liquid or weight/solid) of the depletable chemical in the replenishment reservoir, wherein when the measured amount is below a predetermined minimum amount, the control unit is configured to instruct the user to refill the replenishment reservoir with an additional amount (volume/weight) of the depletable chemical.

As mentioned above, the system of the invention comprises several units. These units may communicate using wired or wireless communication modules, as will be appreciated by those skilled in the art.

In some embodiments, the depletable chemical agent may be a polymeric agent containing an amine nitrogen atom in multiple functional groups that are not necessarily identical and may be combined (e.g., a primary amine, a secondary amine, a tertiary amine, or a quaternary ammonium salt, which may be linear, branched, or cyclic).

In some embodiments, the depletable chemical agent may be a polymeric agent having a relatively high charge density.

In some embodiments, the depletable chemical may be a polymer agent having a molecular weight equal to or greater than 10,000 g/mole.

In some embodiments, the depletable chemical agent may be a polymeric agent having at least one of: (a) a positive charge density of at least 3meq/g of said agent and an average molecular weight of at least 5,000, (b) a positive charge density of at least 6meq/g of said agent and an average molecular weight of at least 1,000, (c) a nitrogen content of at least 1% by weight and an average molecular weight of at least 50,000, and (d) a nitrogen content of at least 18% by weight and an average molecular weight of at least 10,000.

In some embodiments, the depletable chemical agent may be a polymeric agent having:

(1) a nitrogen content of at least 1 wt%, and at least one of:

(a) a positive charge density of at least 3meq/g chemical agent and an average molecular weight of at least 5,000;

(b) a positive charge density of at least 6meq/g chemical agent, and an average molecular weight of at least 1000; and

(2) A nitrogen content of at least 18 wt% and an average molecular weight of at least 10,000.

In some embodiments, the depletable chemical agent may be a polymeric agent having a positive charge density.

In some embodiments, the positive charge density may be at least 0.5meq/g of said agent, at least 1meq/g of said agent, at least 2meq/g of said agent, at least 3meq/g of said agent, at least 4meq/g of said agent, at least 5meq/g of said agent, 6meq/g of said agent, at least 7meq/g of said agent, at least 8meq/g of said agent, at least 9meq/g of said agent, at least 10meq/g of said agent, at least 11meq/g of said agent, at least 12meq/g of said agent, at least 13meq/g of said agent, at least 14meq/g of said agent, at least 15meq/g of said agent, at least 16meq/g of said agent, at least 17meq/g of said agent, at least 18meq/g of said agent, at least 19meq/g of said agent, or at least 20meq/g of said agent.

In some embodiments, the depletable chemical agent may be a polymer agent having the following average molecular weight: at least 500, at least 800, at least 1,000, at least 1,300, at least 1,700, at least 2,000, at least 2,500, at least 3,000, at least 3,500, at least 4,000, at least 4,500, at least 5,000, at least 10,000, at least 15,000, at least 20,000, at least 25,000, at least 50,000, at least 100,000, at least 150,000, at least 200,000, at least 250,000, at least 500,000, at least 750,000, at least 1,000,000, or at least 2,000,000.

In some embodiments, the depletable chemical agent may be a polymeric agent having an average molecular weight of at least 2,000, at least 10,000, or at least 25,000.

In some embodiments, the depletable chemical agent may be a polymeric agent comprising one or more nitrogen atoms that may be positively charged.

As used herein, the term "positively chargeable polymer" or "positively chargeable group" means that a proton (e.g., -NH) can be readily added₂) Or has a permanent positive charge (e.g., -N (CH)₃)₃ ⁺) A polymer or chemical moiety of (a). In some embodiments, these terms refer to inherent characteristics of the polymer or moiety, and thus may encompass polymers or moieties in environments where such protons are added, as well as polymers in environments where such protons are not added. In contrast, a "positively charged" polymer or group refers to a polymer or group that is in an environment to which one or more such protons have been added or that has a permanent positive charge. In some embodiments, the one or more chargeable nitrogen atoms of the depletable chemical agent are selected from the group consisting of: primary, secondary and tertiary amines and quaternary ammonium groups and combinations of such groups. In some embodiments, such groups are covalently bound to and/or form part of a polymer backbone. In some embodiments, the one or more nitrogen atoms are part of a cyclic moiety.

In some embodiments, the one or more nitrogen atoms comprise at least 1 wt.%, at least 1.4 wt.%, at least 2 wt.%, at least 5 wt.%, at least 8 wt.%, at least 10 wt.%, at least 15 wt.%, at least 18 wt.%, at least 20 wt.%, at least 24 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, or at least 50 wt.% of the depletable chemical agent.

In some embodiments, the depletable chemical is a composition comprising poly (diallyldimethylammonium chloride)A polymeric agent of units.

In some embodiments, the depletable chemical agent is a composition comprising polyallylamineA polymeric agent of units.

In some embodiments, the depletable chemical is a composition comprising poly (4-vinylpyridine)A polymeric agent of units.

In some embodiments, the depletable chemical polymer agent is selected from the group consisting of: linear polyethylenimine, branched polyethylenimine, modified polyethylenimine, poly (diallyldimethylammonium chloride), poly (4-vinylpyridine), polyallylamine, vinylpyrrolidone-dimethylaminopropylmethacrylamide copolymer (Viviprint 131), vinylcaprolactam-dimethylaminopropylmethacrylamide hydroxyethyl methacrylate copolymer (Viviprint 200), vinylpyrrolidone and quaternized copolymer of dimethylaminoethyl methacrylate with diethyl sulfate (Viviprint 650), guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride.

In some embodiments, the depletable chemical polymer agent is Polyethyleneimine (PEI) (e.g., Loxanol P, Loxanol MI 6730)

In some embodiments, the concentration (e.g., the first amount) of the depletable chemical polymer agent in the formulation (in the liquid reservoir) is equal to or less than about 5 wt.%, 4 wt.%, 3 wt.%, 2 wt.%, 1 wt.%, 0.5 wt.%, 0.4 wt.%, 0.3 wt.%, 0.2 wt.%, 0.1 wt.%, or equal to or at least about 0.01 wt.%, sometimes at least about 0.05 wt.%.

In some embodiments, the depletable chemical is PEI and its first amount is a concentration by weight in the formulation (in the liquid reservoir) of at least 0.01%, at least 0.05%, at least 0.10%, at least 0.15%, or at least 0.20%.

In some embodiments, the depletable chemical is PEI, and the predetermined threshold is a concentration by weight in the formulation (in the liquid reservoir) of at least 0.01%, at least 0.05%, at least 0.10%, at least 0.15%, or at least 0.20%.

In some non-limiting embodiments according to the invention, the first amount of PEI (in the liquid reservoir) may be 0.25 concentration by weight in the treatment formulation (e.g., 0.75gr PEI in the liquid reservoir holding 300L of treatment formulation). The second amount of PEI (in the replenishment reservoir) may be 25 wt% (e.g., in water). When the first amount of PEI (in the liquid reservoir) decreases below a predetermined threshold, such as 0.01 wt% (e.g., below which the PEI no longer plays its functional capacity during printing), the methods and systems of the present invention are configured to transfer a portion of a second amount of the PEI from the replenishment reservoir into the liquid reservoir to thereby replenish the amount of PEI (in the liquid reservoir) to a value equal to or above the predetermined threshold (e.g., a value equal to 0.01 wt% or above 0.01 wt%), or to replenish the amount of PEI (in the liquid reservoir) to a value equal to the first amount, such as 0.25 wt% (the latter being an example of x100 fold dilution required for PEI when transferring from the replenishment reservoir into the liquid reservoir, i.e., transferring a 3L supplemental 25 wt% solution into a 300L liquid formulation of the liquid reservoir).

In some embodiments, the depletable chemical is PEI and its first amount is a concentration by weight in the formulation (in the liquid reservoir) of at most 6%, at most 5%, at most 4%, at most 3%, at most 2.5%, at most 2.0%.

In some embodiments, the depletable chemical is PEI and the first amount thereof is a concentration by weight in the formulation (in the liquid reservoir) in the range of 0.01 to 1%, 0.01 to 0.8%, 0.01 to 0.7%, 0.01 to 0.6%, 0.1 to 0.5%, 0.2 to 0.7%, 0.2 to 0.6%, or 0.2 to 0.5%.

In some embodiments, the PEI has an average molecular weight of at least 20,000, at least 50,000, at least 100,000, at least 200,000, at least 350,000, at least 500,000, at least 700,000, at least 750,000, and optionally up to 3,000,000, up to 2,500,000, or up to 2,000,000.

In some embodiments, the PEI has an average molecular weight of 750,000.

In some embodiments, the depletable chemical is a polymeric agent that is PEI, and wherein the PEI is a surfactant, a wetting agent, an anchoring agent, or any combination thereof.

In some embodiments, the PEI is a surfactant.

In some embodiments, the PEI is a wetting agent.

In some embodiments, the PEI is an anchoring agent.

In some embodiments, the PEI polymer has a charge density in the range of 16-20meq/g of material.

In some embodiments, the PEI has a charge density of 8 meq/g.

In some embodiments, the depletable chemical is a silicone-functionalized PEI [ e.g., X223939 a (shin edsu) ], for example the silicone functionality has the following structure:

in some embodiments, the depletable chemical is a quaternary ammonium compound.

In some embodiments, the quaternary ammonium compound is Larostat264A (BASF).

In some embodiments, the quaternary ammonium compound is Foamquat SAQ (linoleamidopropyl ethyl dimethyl ammonium ethyl sulfate 90).

In some embodiments, the depletable chemical agent is water dispersible (e.g., polymeric water dispersible).

In some embodiments, the depletable chemical is water soluble (e.g., a water soluble polymer).

In some embodiments, the depletable chemical is a solid at room temperature.

In some embodiments, at least one binder in the ink formulation is an anionic binder, such as an acrylic binder and/or a sulfonic acid binder. Similar anionic binders are within the scope of the invention.

In some embodiments, at least one binder in the ink formulation is a negatively charged organic polymeric resin.

In some embodiments, the negatively charged organic polymer resin has an average molecular weight of at least 8,000.

In some embodiments, at least one binder in the ink formulation is an acrylic polymer and/or an acrylic-styrene copolymer (e.g., having an average molecular weight of about 60,000 g/mole).

In some embodiments, at least one binder in the ink formulation is 538 BASF。

In some embodiments, the depletable chemical is PEI, and the reduction in its first amount is due to an undesired side reaction with the at least one basic binder (e.g., a basic binder having COO-or SOOO-groups as side chains).

In some embodiments, the formulation (in the liquid reservoir) may further comprise at least one competitor component that is inert with respect to the printing process, i.e., does not have functionality in itself during the printing process, wherein the competitor is selected to rapidly interact (relative to the depletable chemical) with one or more contaminating components (e.g., binder) of the ink, thereby preventing or minimizing the depletion of the depletable chemical (e.g., PEI) as it is the competing component (rather than the depletable chemical) that interacts with the contaminating ink components (e.g., ink binder). A non-limiting example of such competing ingredients is a polyanionic material.

To this end, in some embodiments, the system may further comprise means for removing products generated between the at least one competitive component and the one or more contaminant ink components.

In some embodiments, the system of the present invention is used for indirect printing, wherein the system further comprises:

i. an Intermediate Transfer Member (ITM) comprising a release layer surface;

a treatment station comprising a liquid reservoir configured for holding an aqueous treatment formulation as disclosed herein, the treatment station configured for applying the aqueous treatment formulation to a release layer surface of the ITM to form a treatment layer thereon;

a replenishment unit comprising a replenishment reservoir as disclosed herein.

An image forming station configured to apply a printing liquid to form an image on an aqueous treatment formulation formed on the intermediate transfer member;

v. a transfer station for transferring the image onto the printing substrate, for example by pressure contact between the ITM and the printing substrate.

In some embodiments, the printing liquid is an ink, optionally applied by jetting, and the system further comprises:

In some embodiments, in the methods of the present invention, the liquid formulation is configured to be applied to a substrate on which an image is to be printed, or to an intermediate transfer member in an indirect printing process.

In some embodiments, the method of the present invention is used in an indirect printing process, wherein the method further comprises:

i. providing an Intermediate Transfer Member (ITM);

providing a treatment formulation as disclosed herein;

applying the treatment formulation onto the image receiving surface of the ITM to form a wet treatment layer;

at least partially drying the wet treated layer to form an at least partially dried treated layer;

v. applying a printing liquid onto the at least partially dried treatment layer to form an image;

transferring the image onto a printing substrate by pressurized contact between the surface of the ITM and the printing substrate.

In some embodiments, the printing liquid is an ink, optionally an aqueous ink, and the method further comprises:

applying ink drops on the at least partially dried treatment layer to form an ink image; and

at least partially drying the wet ink image on the aqueous treatment layer to form a partially dried ink image film to be transferred to the printing substrate.

FIG. 1B provides an illustration of an exemplary printing system of which the system of the present invention may form a part. In particular, fig. 1B is a schematic side view of an electronic printing system 10 according to some embodiments of the present invention. In some embodiments, the system 10 includes a rolling flexible blanket 12 that may be cycled between an image forming station 14, a drying station 16, an embossing station 18, and a blanket processing station 20.

As used herein, the term "blanket" refers to a flexible transfer member that may be mounted within a printing apparatus to form a belt-like structure on two or more rollers, wherein at least one roller is capable of rotating and moving the blanket (e.g., by moving its belt) so that it travels around the roller.

As used herein, the terms "cover layer" and "intermediate transfer member" (ITM) are used interchangeably and refer to a flexible member that includes at least a release layer that serves as an intermediate member configured to receive and transfer an ink image to a target substrate, as detailed herein.

In the operational mode, the image forming station 14 is configured to form a mirror ink image of the digital image on an upper run of the surface of the cover layer 12, which is also referred to herein as an "ink image" (not shown). The ink image is then transferred to a target substrate (e.g., paper, folding carton, or any suitable flexible packaging in sheet or continuous web form) positioned under the lower run of the cover layer 12.

As used herein, the terms "ink image" and "image" are interchangeable. Sometimes, the term refers to a printed image formed on the cover layer 12 and transferred to the target substrate. Sometimes, they refer to the image on the substrate (e.g., paper, folding carton, or any suitable flexible package in sheet or continuous web form) itself. Accordingly, these terms should be interpreted in the context in which they are used.

As used herein, the term "row segment" refers to a length or section of the cover layer 12 between any two given rollers over which the cover layer 12 is guided.

In some embodiments, the cover layer 12 may be adhered (e.g., sewn) edge-to-edge during installation to form a continuous cover layer loop (not shown). Examples of methods and systems for installing seams are detailed in U.S. provisional application 62/532,400, the disclosure of which is incorporated herein by reference.

In some embodiments, the image forming station 14 generally includes a plurality of print bars 22, each mounted (e.g., using a slide) on a frame (not shown) positioned at a fixed height above the surface of the upper run of the cover layer 12. In some embodiments, each print bar 22 includes a print head strip (strip of print heads) that is as wide as the print area on the cover layer 12 and includes individually controllable print nozzles.

In some embodiments, the image forming station 14 may include any suitable number of strips 22, each strip 22 may contain a printing fluid, such as a different color aqueous ink. The inks typically have visible colors such as, but not limited to, cyan, magenta, red, green, blue, yellow, black, and white. In the example of fig. 1B, the image forming station 14 includes 7 print bars 22, but may include, for example, 4 print bars 22 of any selected color, such as cyan, magenta, yellow, and black.

In some embodiments, the print head is configured to eject ink drops of different colors onto the surface of the cover layer 12, thereby forming an ink image (not shown) on the surface of the cover layer 12.

In some embodiments, the different print bars 22 are spaced apart from one another along an axis of movement of the cover layer 12, represented by arrow 24. In this configuration, precise spacing between the stripes 22 and synchronization between the ink drops guiding each stripe 22 and the moving cover layer 12 are critical to achieving proper placement of the image pattern.

In some embodiments, the system 10 includes a heater, such as a hot air or air blower 26, positioned between the print bars 22 and configured to partially dry ink droplets deposited on the surface of the cover layer 12.

Such a flow of hot air between the print bars may help, for example, reduce condensation at the print head surface and/or condensation in the process satellites (e.g., residue or droplets distributed around the main ink droplets), and/or prevent clogging of the print head inkjet nozzles, and/or prevent unwanted merging of ink droplets of different colors on the cover layer 12 with one another. In some embodiments, the system 10 includes a drying station 16 configured to blow hot air (or another gas) onto the surface of the cover layer 12. In some embodiments, the drying station comprises an air blower or any other suitable drying device.

In the drying station 16, the ink image formed on the cover layer 12 is exposed to radiation and/or hot air to more thoroughly dry the ink, thereby evaporating most or all of the liquid carrier and leaving only a layer of resin and colorant, which is heated to the point of presenting a tacky ink film.

In some embodiments, the system 10 includes an overburden transport assembly 26 configured to move a rolling ITM, such as the overburden 12. In some embodiments, the blanket transport assembly 26 includes one or more rollers 28, wherein at least one roller 28 includes an encoder (not shown) configured to record the position of the blanket 12 so as to control the position of a portion of the blanket 12 relative to the respective print bar 22. In some embodiments, the encoders of the rollers 28 generally comprise rotary encoders configured to generate rotation-based position signals indicative of the angular displacement of the respective rollers.

Additionally or alternatively, the overlay 12 may include integrated encoders (not shown) for controlling the operation of the various modules of the system 10. The integrated encoder is described in detail, for example, in U.S. provisional application 62/689,852, the disclosure of which is incorporated herein by reference.

In some embodiments, the system 10 includes an embossing station 18, wherein the blanket 12 passes between an embossing cylinder 30 and a pressure cylinder 32 configured to carry the compressible blanket.

In some embodiments, system 10 includes a console (not shown) configured to control the various modules and components of system 10.

In some embodiments, the blanket treatment station 20, which may also function as a cooling station, is configured to treat the blanket, for example, by cooling the blanket and/or applying a treatment fluid to the outer surface of the blanket 12, and/or cleaning the outer surface of the blanket 12. The treatment may be performed by passing the cover layer 12 through one or more rollers or blades configured to apply a cooling and/or cleaning and/or treatment fluid on the outer surface of the cover layer.

In the example of FIG. 1B, the station 20 is mounted between two particular rollers 28, however the station 20 may be mounted adjacent the cover layer 12 at any other suitable location between the impression station 18 and the image forming station 14.

In some embodiments, the liquid receptacle of the system of the present invention forms part of station 20.

In some embodiments, the replenishment receptacle of the system of the present invention forms part of station 20.

In some embodiments, the impression cylinders 30 of the impression station 18 are configured to imprint an ink image onto a target substrate, such as a single sheet 34 that is transferred by a substrate transport module 36 (shown schematically) from an input stack 38 to an output stack 40 via the impression cylinders 30. In some embodiments, the target substrate may comprise any suitable substrate, such as, but not limited to, a flexible substrate, a partially flexible substrate (e.g., having a flexible portion and a rigid portion), or a rigid substrate.

In some embodiments, system 10 includes an additional embossing station (not shown) to allow for two-sided printing (i.e., printing on both sides of sheet 34).

In alternative embodiments, different configurations of the substrate conveyor 36 may be used to print on a continuous web substrate. Detailed descriptions and various configurations of single-sided and double-sided printing systems that provide feed sheets and systems for printing on continuous web substrates are provided in, for example, U.S. patents 9,914,316 and 9,186,884, PCT international publication WO 2013/132424, U.S. patent application publication 2015/0054865, and U.S. provisional application 62/596,926, the disclosures of each of which are incorporated herein by reference.

A particular configuration of the system 10 is shown by way of example. However, embodiments of the present invention are in no way limited to this particular type of exemplary system, and the principles described herein are equally applicable to any other type of printing system.

In some embodiments, the formulation, such as the treatment formulation (in the liquid reservoir), may further comprise one or more of the following: (a) at least one water-soluble polymer; (b) at least one surfactant; (c) at least one humectant and (d) at least one humectant.

In some embodiments, the formulation, such as the treatment formulation (in a liquid reservoir), may further comprise at least one particulate material selected from the group consisting of: (i) at least one thermoplastic polymer particulate material; (ii) at least one thermoset polymer particulate material; or (iii) combinations thereof.

As used herein, the term "thermoset polymeric particulate material" or any of its language variants refers to a particulate material that is a polymeric material (e.g., a relatively high molecular weight polymeric material) that becomes irreversibly hardened after curing, such as by the action of heat or suitable radiation. Once hardened, this material cannot be re-melted.

Non-limiting examples of thermoset polymer particulate materials are Polytetrafluoroethylene (PTFE), Perfluoroalkoxyalkane (PFA), or Fluorinated Ethylene Propylene (FEP).

In some embodiments, the thermoset polymer particulate material is PTFE.

As used herein, the term "thermoplastic polymeric particulate material" or any other language variation thereof refers to a particulate material that is a polymeric material (e.g., a relatively high molecular weight polymeric material) that becomes pliable or moldable above a particular temperature and solidifies upon cooling. This material can be remelted and reshaped.

A non-limiting example of a thermoplastic polymer particulate material is a wax particulate material.

In some embodiments, the wax particulate material is an oxidized polyethylene wax particulate material.

In some embodiments, the wax particulate material is a coated wax particulate material.

In some embodiments, the coated wax particulate material is a wax particulate material coated with silica.

Treatment formulations comprising such particulate materials are disclosed in U.S. provisional application No.62/787,984, U.S. provisional application No.62,825,568, and international application No. pct/IB2020/050001, the contents of each of which are incorporated herein by reference.

In some embodiments, the formulation, such as the treatment formulation (in the liquid reservoir), may further comprise at least one modified polysaccharide (such as cellulose derivatives, cellulose ethers, methylcellulose, and hydroxypropylmethylcellulose).

As used herein, the term "modified polysaccharide" refers to a polymeric carbohydrate molecule comprised of long chains of monosaccharide units bonded together by glycosidic linkages, wherein at least one hydrogen atom of a hydroxyl group in a monosaccharide unit is replaced by another group (e.g., R).

Treatment formulations comprising such modified polysaccharides are disclosed in U.S. provisional application No. 62/790,890, U.S. provisional application No.62,825,568, and international application No. PCT/IB2020/050001, the contents of each of which are incorporated herein by reference.

In some embodiments, the formulation (in the liquid reservoir) optionally may further comprise at least one antibacterial agent.

In some embodiments, a formulation (in a liquid reservoir), such as a treatment formulation, comprises:

at least one water-soluble polymer;

an aqueous carrier liquid; and

optionally, one or more of the following: (a) at least one humectant; (b) at least one surfactant and (c) at least one wetting agent.

In some embodiments, the water soluble polymer may be at least one modified polysaccharide (such as cellulose derivatives, cellulose ethers, methylcellulose, and hydroxypropylmethylcellulose).

In some embodiments, the modified polysaccharide is hydroxypropyl methylcellulose.

In some embodiments, the water soluble polymer may be selected from the group consisting of: polyvinyl alcohol, water-soluble cellulose, polyvinylpyrrolidone (PVP), polyethylene oxide, and water-soluble acrylate.

In some embodiments, the water-soluble polymer may be a polyethylene oxide chain (PEO) or polypropylene oxide chain (PPO) based polymer.

In some embodiments, the concentration of the water-soluble polymer in the formulation (in the liquid reservoir) may be in the range 0.5 to 8%, 2.5 to 6.5%, 2.5% to 6%, 2.5 to 5.5%, or 2.5 to 5%, optionally up to 10% or up to 8% or up to 6% or up to 5%.

In some embodiments, the at least one water soluble polymer (in the liquid receptacle) has a solubility in water at 25 ℃ of at least 2%, at least 7%, at least 10%, at least 12%, at least 15%, at least 20%, or at least 25%, and optionally, at most 80%, or at most 60%.

In some embodiments, the surfactant may be a nonionic surfactant, such as a nonionic silicone-containing surfactant.

In some embodiments, the formulation (in the liquid reservoir) has a total surfactant concentration of at least 0.3%, at least 0.5%, at least 0.75%, at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, and optionally in the range of 6 to 40%, 6 to 30%, 6 to 20%, 7 to 30%, 7 to 20%, 7 to 15%, 8 to 25%, 8 to 20%, 8 to 15%, 8 to 13%, 9 to 25%, 9 to 20%, 9 to 15%, 9 to 13%, 10 to 25%, 10 to 20%, 10 to 15%, or 10 to 13%.

In some embodiments, the formulation (in the liquid reservoir) contains at least 6 wt.%, at least 7 wt.%, at least 8 wt.%, at least 9 wt.%, or at least 10 wt.% of the nonionic surfactant.

In some embodiments, the formulation (in the liquid reservoir) contains at most 18 wt.%, at most 16 wt.%, at most 15 wt.%, at most 14 wt.%, or at most 13 wt.% of the nonionic surfactant.

In some embodiments, the concentration of the nonionic surfactant within the formulation (in the liquid reservoir) is in the range of 0.5% -18%, 1-18%, 2-16%, 6.5-18%, 6.5-16%, 7.5-18%, 7.5-16%, 8.5-18%, 8.5-16%, 9.5-18%, 9.5-16%, 10.5-18%, or 10.5-16% by weight.

In some embodiments, the solubility of the nonionic surfactant in water at 25 ℃ is at least 2%, at least 8%, at least 10%, at least 12%, at least 15%, at least 20%, at least 25%, or at least 30%, and optionally, at most 80%, or at most 60%.

In some embodiments, the nonionic surfactant is a polyethoxylated sorbitan ester.

In some embodiments, the polyethoxylated sorbitan ester comprises at least one material or at least two materials selected from the group consisting of: PEG-4 sorbitan monolaurate, PEG-20 sorbitan monopalmitate, PEG-20 sorbitan monostearate and PEG-20 sorbitan monooleate.

In some embodiments, the HLB value of the nonionic surfactant is at least 11, at least 12, at least 13, at least 14, or at least 14.5, and optionally at most 22, at most 21, at most 20, at most 19, at most 18, or at most 17, and further optionally, in the range of 11 to 25, 11 to 23, 11.5 to 21, 11.5 to 20, 11.5 to 18, 12.5 to 21, 12.5 to 20, 12.5 to 18, 13.5 to 21, 13.5 to 20, 13.5 to 18, 14 to 20.5, 14 to 18.5, 14.5 to 20, 14.5 to 19, 14.5 to 18, or 14.5 to 17.5.

In some embodiments, the formulation (in the liquid reservoir) contains at least 6 wt.%, at least 7 wt.%, at least 8 wt.%, at least 9 wt.%, or at least 10 wt.% of the nonionic surfactant.

In some embodiments, the formulation (in the liquid reservoir) contains at most 18 wt.%, at most 16 wt.%, at most 15 wt.%, at most 14 wt.%, or at most 13 wt.% of the nonionic surfactant.

In some embodiments, the nonionic surfactant within the formulation (in the liquid reservoir) is in the range of 2-18%, 5.5-16%, 6.5-18%, 6.5-16%, 7.5-18%, 7.5-16%, 8.5-18%, 8.5-16%, 9.5-18%, 9.5-16%, 10.5-18%, or 10.5-16% by weight.

In some embodiments, the concentration of the nonionic surfactant within the treatment formulation (in the liquid reservoir) is in the range of 2-18%, 1-15%, 1-12%, 1-10%, 1-8%, 2-18%, 2-15%, 2-12%, 2-10%, 2-8%, 3-18%, 3-15%, 3-12%, 3-10%, 3-8%, or 4-18%, 4-15%, 4-12%, 4-10%, or 4-8% by weight.

In some embodiments, the formulation (in the liquid reservoir) comprises a further non-ionic silicone-containing surfactant selected from polysiloxane-polyoxyalkylene copolymers, and wherein optionally the concentration of the polysiloxane-polyoxyalkylene copolymer is at least 0.3 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1.0 wt.%, and further optionally at most 5 wt.%, at most 4 wt.%, at most 3 wt.%, at most 2.5 wt.%, at most 2 wt.%, or at most 1.75 wt.%.

In some embodiments, the formulation (in the liquid reservoir) contains at least 0.3 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1.0 wt.%, and optionally, at most 5 wt.%, at most 4 wt.%, at most 3 wt.%, at most 2.5 wt.%, at most 2 wt.%, or at most 1.75 wt.% of a further nonionic silicone-containing surfactant.

In some embodiments, the further nonionic silicone-containing surfactant comprises a polysiloxane-polyoxyalkylene copolymer, and wherein optionally the concentration of the polysiloxane-polyoxyalkylene copolymer is at least 0.3 wt.%, at least 0.5 wt.%, at least 0.75 wt.%, or at least 1.0 wt.%, and further optionally at most 5 wt.%, at most 4 wt.%, at most 3 wt.%, at most 2.5 wt.%, at most 2 wt.%, or at most 1.75 wt.%.

In some embodiments, the formulation (in the liquid reservoir) has a total surfactant concentration of at least 2%, at least 6%, at least 7%, at least 8%, at least 10%, or at least 12%, and optionally in the range of 6 to 40%, 6 to 30%, 6 to 20%, 7 to 30%, 7 to 20%, 7 to 15%, 8 to 25%, 8 to 20%, 8 to 15%, 8 to 13%, 9 to 25%, 9 to 20%, 9 to 15%, 9 to 13%, 10 to 25%, 10 to 20%, 10 to 15%, or 10 to 13%.

In some embodiments, the formulation (in the liquid reservoir) comprises at least one wetting agent.

In some embodiments, the wetting agent is PEI.

In some embodiments, the PEI is one or more PEI's detailed in table 1 below:

table 1: exemplary PEI

In some embodiments, the PEI is in an aqueous solution (A)PS, BASF).

Non-limiting examples of suitable exhaustible chemicals are N-Hance BF 17 cationic guar, N-Hance CCG 45 cationic guar, N-Hance HPCG 1000 cationic guar, N-Hance BF 13 cationic guar, N-Hance CG 13 cationic guar, N-Hance 3196 cationic guar (all from Ashland Specialty Ingredients)

In some embodiments, the depletable chemical is guar hydroxypropyltrimonium chloride (GHPTC).

In some embodiments, the depletable chemical is hydroxy guar hydroxypropyl trimonium chloride (HGHPTC).

Further non-limiting examples of suitable depletable chemicals are listed in table 2 below:

table 2: exemplary exhaustible chemical Agents

Chemical agent (brand name)]	Charge density, meq/g	Molecular weight
			Poly (diallyldimethylammonium chloride)	-6 (calculated value)	200,000-300,000
Poly (4-vinylpyridine)	7 (calculated value)	60,000-160,000
			Polyallylamine	17.5 (Calculations)	17,000

Further non-limiting examples of suitable depletable chemicals are listed in table 3 below:

table 3: exemplary exhaustible chemical Agents

A chemical agent, which is a chemical agent,	material	Viscosity of the oil	Density of electric charge
				Lupasol PS	PEI		Is very high
CG 13	GHPTC	Height of	In
				BF 13	GHPTC	Height of	In
3196	GHPTC	Height of	In
				BF 17	GHPTC	Height of	Is very high
CCG 45	GHPTC	Is low in	In
				Hpcg 1000	HGHPTC	In	In

Further details of treatment formulations suitable for use in the methods and systems according to the present invention are disclosed in, for example, WO 2013/132418, WO 2013/132339 and WO 2019/111223, the contents of each of which are incorporated herein by reference.

Further details of non-limiting examples of ink compositions suitable for use in the printing processes and systems of the present invention are disclosed in WO 2013/132439, PCT/IB13/51755(WO 2013/132439) or US2015/0025179, PCT/IB14/02395(WO 2015/036865) or US14/917461, all of which are incorporated herein by reference.

In some embodiments, formulations, e.g., treatment formulations and ink formulations, are as disclosed and exemplified herein.

It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination or as suitable in any other described embodiment of the invention.

Detailed description of the embodiments

The following examples are not intended to limit the scope of the invention as claimed in any way.

Example 1: aqueous treatment preparation

Exemplary aqueous treatment formulations used in this study and referred to herein as V1, V2, and V3 are provided in tables 4,5, and 6, respectively.

Treatment formulation V1 was prepared by mixing the ingredients listed in table 4 herein below:

table 4: treatment formulation V1

Composition (I)	Concentration (% w/w)	Action of ingredients
			PVA 6-88	3.75％	Water-soluble polymers
BYK LPX 23289	1.50％	Surface active agent
			Loxanol P	0.25％	Wetting agent
Candy	6.50％	Moisture-retaining agent
			Tego 280	1.10％	Surface active agent
Tween20	12.00％	Surface active agent
			K12N	0.20％	Antibacterial agents
Water (W)	74.7％

Treatment formulation V2 was prepared by mixing the ingredients listed in table 5 herein below:

table 5: treatment formulation V2

Treatment formulation V3 was prepared by mixing the ingredients listed in table 6 herein below:

table 6: treatment formulation V3

It should be noted that the ingredients of the treatment formulation according to the present invention may be mixed in any suitable manner to form a composition that may be applied as a coating to an intermediate transfer member. Sometimes the mixed ingredients may form a dispersion. To this end, the system of the present invention is configured to provide a mixing tool to provide a uniform dispersion of the treatment formulation.

Example 2: ink formulations

Pigment preparation

The pigments used in the examples described below generally have an initial particle size of a few microns. Such pigments are ground in the presence of a dispersant into the submicron range, the two materials being fed as an aqueous mixture into a milling apparatus (bead mill). The milling schedule is controlled based on particle size measurements (e.g., Malvern or Nanosizer instruments). When average particle size (d)_V50) When 70 to 100nm is reached, milling is stopped.

Exemplary ink compositions

In this example, the preparation of an ink composition is described: as previously mentioned, willBlue D7079 and190 and mixing the materials in the following proportions:

will D_VThe milled concentrate, which is less than 50nm, typically between 70 and 100nm, is further diluted with 50g of water and extracted from the milling apparatus with a pigment concentration of about 12% by weight. The millbase (milibase) concentrate is further processed as described below for the preparation of the ink composition.

In the first stage, 2.4g of sodium dodecanoate were added to 200g of millbase concentrate to obtain the millbase. The mixture was stirred to homogeneity (5' magnetic stirrer stirring at 50 rpm) and incubated at 60 ℃ for 1 day. The mixture was then allowed to cool to ambient temperature.

In the second stage, the ink ingredients were added to the mill base as follows:

the mixture was stirred at ambient temperature for 30 minutes to give an ink jettable ink composition with a viscosity of less than 10 cP.

Example 3: study of factors affecting the Life of treatment formulations

A treatment formulation stock in an amount of about 200L was prepared.

During the printing process, approximately 0.5g of treatment formulation was consumed per printed page in order to apply the ITM.

The treatment formulation needs to be replenished with an additional amount of treatment formulation (including all ingredients) based on the amount consumed (about 100L per week for a total of about 300L, with a total replenishment rate of about 300L/month).

The inventors of the present invention have realized that the treatment formulation needs to be replenished in a very frequent manner, which does not reflect the need to replenish the treatment formulation on a calculation of 0.5g of treatment formulation per printed page.

To minimize (zero) the use of treatment formulations other than the printing needs, the effect of various factors was tested as detailed below:

viscosity and surface tension measurements:

the viscosity and surface tension of the treatment formulations were tested at room temperature and 50 ℃ for a period of 6 months.

The results are shown in FIGS. 2 and 3.

Fig. 2 shows a graph depicting the average viscosity measurements of the treatment formulations as a function of time. Fig. 3 shows a graph depicting the change over time of the mean surface tension measurements for the treatment formulations.

Both fig. 2 and fig. 3 illustrate that the treatment formulation retains its physical properties over a period of time.

Print quality was measured as a function of age and temperature of the treatment formulation:

the print quality of the treatment solutions as a function of age and temperature was investigated.

4A-4C show a portion of a printed image obtained in an indirect printing process using: a freshly prepared treatment formulation (t ═ 0) (fig. 4A), a one month old treatment formulation at room temperature (fig. 4B), and a one month old treatment formulation at 50 ℃ (fig. 4C).

Figures 4A-4C illustrate that no change in print quality was observed as a result of aging of the treatment formulation (up to 1 month) and that the formulation maintained its performance characteristics for at least 1 month at both room temperature and 50 ℃.

Print quality was measured as a function of the utilization of the treatment formulation:

problematic treatment formulations from printing presses were tested which had low print quality as determined based on print particle size.

No difference in their physical properties was measured compared to the freshly prepared treatment formulations.

Fig. 5A-5B show printed images obtained during an indirect printing process using fresh treatment formulation that has not been used before (fig. 5A) and treatment formulation that has been used for multiple printing cycles during the printing process (fig. 5B).

Figures 5A-5B clearly illustrate the low image quality produced with the used treatment formulation.

Print quality was measured as a function of the utilization of the treatment formulation and as a function of the aging of the overlay:

the effect of aging of the cover layer and the combination of the cover layer with the treatment formulation from the printing press were tested.

Fig. 6A-6D show printed images and enlarged (magnified) portions thereof obtained in an indirect printing process using the following combinations: fresh blanket, fresh treatment formulation (fig. 6A); fresh blanket, used treatment formulation (fig. 6B); aged overlay, fresh treatment formulation (fig. 6C); and aged cover, used treatment formulation (fig. 6C).

Fig. 6A-6D illustrate that high image particle size indicates poor quality of the treatment solution, requiring renewal of the stock of treatment formulation in the press. Sometimes, the renewal is not sufficient to minimize the granularity of the image and requires a complete change of the treatment formulation during the printing process.

Effect of age and temperature of treatment formulation on image particle size:

the effect of temperature and aging of the treatment formulations on image quality as reflected by image granularity was tested.

Fresh treatment formulation (not used during printing) was used.

Three time points were determined, t 0, t 1d (one day) and t 3d (three days), and two temperatures, room temperature and 50 ℃.

Experiments with a cover layer aged 2h at 135 ℃ were used.

Particle size-K570, 70%, QEA (K570-black ink 70% -coating percentage of black ink in print, QEA-digital microscope).

Fig. 7 shows a graph depicting the effect of aging (time) and temperature of the treatment formulation on graining of the printed image.

As reflected in fig. 7, the time frame and temperature studied had no effect on the granularity of the image formed.

Ink contamination and filtration effects on image granularity:

the effect of ink contamination on image granularity was tested.

Fresh treatment formulation (not used during printing) was used.

Three time points were identified as t-0, t-1 d (one day) and t-3 d (three days). Two temperatures were studied: room temperature and 50 ℃.

Experiments with a cover layer aged 2h at 135 ℃ were used.

Particle size-K570, 70%, QEA (K570-black ink 70% -coating percentage of black ink in print, QEA-digital microscope).

The ink formulation (YMCK) was introduced into the fresh treatment formulation at 4 wt% and 8 wt%.

Some formulations were filtered as detailed below.

Fig. 8 shows a graph depicting the effect on graining of printed images produced with a treatment formulation with ink contamination at room temperature.

Fig. 9 shows a graph depicting the effect on graining of printed images produced with ink contaminated treatment formulations at 50 ℃.

10A-10D show printed images obtained in an indirect printing process using: fresh TF (fig. 10A), ink contaminated TF stored at 50 ℃ for 3 days (fig. 10B), filtered fresh TF contaminated with ink at room temperature (fig. 10C) and filtered TF contaminated with ink stored at 50 ℃ for 3 days (fig. 10D).

Figures 8, 9 and 10A-10D clearly show that ink contamination has a significant negative impact on the treatment formulation properties essential to the printing process, as reflected in the increase in particle size observed for images produced with treatment formulations having ink formulations incorporated therein. Negative effects of ink contamination on the properties of the treatment formulations were observed at both room temperature and 50 ℃. Filtering contaminated treatment formulations does not improve the performance of the treatment formulations.

Over time, it was noted that a low print quality was also observed in the case of the freshly prepared treatment formulation (zero) into which the ink formulation was introduced (fig. 8), i.e. the negative effects of ink contamination were immediately generated. This negative effect cannot be corrected by filtering the ink contaminated treatment formulation (fig. 10C).

Impact of ink contamination on PEI Performance:

the above results indicate that while aging of the treatment formulation and its temperature do not affect its performance, ink contamination severely affects the functional capabilities of the treatment formulation, resulting in the need to renew the treatment formulation (i.e., the need to add fresh treatment formulation to the liquid reservoir holding the treatment formulation during printing). Sometimes, the quality of the treatment formulation is so compromised that it needs to be discarded.

Filtering contaminated treatment formulations does not offset the negative effects of ink contamination, which means that the reaction between the ink components and the treatment formulation affects the quality of the treatment formulation.

The inventors investigated the possibility that a reduction in the amount of the chemical PEI in the treatment formulation will affect its quality. In particular, the inventors investigated whether a reduction in its amount would negatively affect the wetting of the treatment formulation, which is necessary for its good performance.

FIGS. 11A-11B show images of polyethylene terephthalate (PET) slides coated with treatment formulations containing PEI (FIG. 11A) and without PEI (FIG. 11B). It is apparent from fig. 11A-11B that the coating was less uniform in the absence of PEI, indicating that there was a wetting problem (decreased wetting ability) in the absence of PEI.

The inventors have surprisingly found that PEI interacts with the binder of the ink formulation. FIG. 12 illustrates that phase separation and precipitation were observed after adding the ink binder Joncryl 538BASF to the PEI solution.

Fig. 13A-13D show images of PET coated with (left side): PEI containing treatment formulation (fig. 13A), PEI free treatment formulation (fig. 13B), TF stored for 3 days and at 50 ℃ contaminated with ink (fig. 13C), and TF contaminated with ink but containing additional amounts of PEI (fig. 13D). Fig. 13A-13D further show (right side) corresponding portions (enlargements) of printed images obtained during indirect printing with corresponding treatment formulations.

FIGS. 13A-13D clearly illustrate the importance of the presence of PEI in the treatment formulation. Its absence results in uneven ITM coating (e.g., wetting problems), which results in poor print quality (fig. 13B). Similar effects were observed with treatment formulations contaminated with ink (fig. 13C). ITM coating non-uniformity was restored only by adding PEI to the contaminated formulation (fig. 13D).

Fig. 14A shows a graph depicting graining of printed images produced during indirect printing with fresh TF, ink-contaminated TF, and ink-contaminated TF with added amounts of PEI. Fig. 14B shows a portion of a corresponding printed image obtained during indirect printing using a corresponding treatment formulation.

FIGS. 15A-15C show printed images produced during indirect printing using fresh TF (FIG. 15A), ink contaminated TF (FIG. 15B), and ink contaminated TF with added amounts of PEI (FIG. 15C). Fig. 15A-15C further illustrate a portion of the corresponding printed image (magnified).

The above results show that PEI alone can restore the performance of the treatment formulation without the need to replenish the entire treatment formulation. These results further illustrate that the reduction in print quality is due to the reduced amount of PEI. This reduction is due to the reaction of the PEI with the binder of the ink formulation.

Without wishing to be bound by theory, the inventors believe that the immediate phase separation and precipitation observed after addition of the ink binder to the PEI solution (fig. 12) may be due to the charge characteristics of the PEI (with a positively charged nature) and the ink binder (with a negatively charged nature) as well as due to the high molecular weight of the PEI that needs to be reacted with the ink binder at low concentrations.

The above results illustrate the importance of the presence of PEI in the treatment formulation. Even a slight decrease in its concentration in the treatment formulation affects the performance of the treatment formulation. Even if the amount of ink contamination in the treatment formulation is relatively small, the functional capability of the treatment formulation is negatively affected.

The results of the above studies indicate that ink contamination of the treatment formulation has a strong negative impact on the performance of the treatment formulation. The properties of the treatment formulations can be repaired by the addition of PEI. This addition counteracts the decrease in PEI concentration in the treatment formulation due to ink contamination resulting in a rapid reaction between the binder of the ink formulation and the PEI. Exhaustion of PEI seriously affects the ITM coating quality and also the quality of the printed image. The results of the above studies are very important and contribute in particular to improving the costs involved in the printing process, since the entire treatment formulation does not need to be replenished, only PEI. Print quality stability can be achieved while reducing unnecessary waste that would otherwise require discarding large quantities of low quality process formulations.

Example 4: detection and quantification of PEI in treatment formulations

To determine whether PEI addition is required to repair its depletion in the treatment formulation, the concentration of PEI in the treatment formulation is measured using spectroscopic tools known in the art, see, for example, the following links:

https://www.sciencedirect.com/science/article/pii/S1878535213001779

https://www.ncbi.nlm.nih.gov/pubmed/12560058

https://onlinelibrary.wiley.com/doi/abs/10.1002/pol.1967.150050816

https://www.researchgate.net/publication/299346733_Validation_of_a_New_Method_for_Spectrophotometric_Determination_of_Polyethyle neimine

in particular, PEI detection is performed using assays that involve reactions with copper. PEI can be detected by the addition of copper ions, which results in blue emission from the solution and strong absorption at 285nm (note that absorption at 650nm can also be used, but its intensity is lower relative to that observed at 285 nm).

The inventors tested various samples of the treatment formulation. 1ml of sample was introduced into a 3ml bottle and 0.1M Cu solution was aspirated. The solution was mixed using a vortex for 3 seconds.

FIG. 16 shows a scheme illustrating PEI detection by the addition of copper ions to a PEI solution, which results in blue emission from the solution and strong absorption at 285 nm.

FIGS. 17A-17L illustrate the color reaction observed after titration with copper of various fresh TF with different concentrations of PEI (the corresponding observed particle size values are recorded numerically on vials containing the titrated TF). FIGS. 17A-17L illustrate that 80. mu.l of 0.1M Cu is sufficient to detect a 1ml sample (above 80ml, no further change in color is observed).

Fig. 18 shows the absorption spectra (PEI + Cu spectra) observed after addition of copper to various TFs with different PEI concentrations (3 ml samples were placed in vials, 20ul of 0.1M Cu solution was added, samples were diluted first to 0.01% and then a second dilution). The final sample was placed in a cuvette and subjected to spectroscopic analysis.

FIG. 19 shows a calibration curve at 285nm generated with treatment formulations with known PEI concentrations in the presence of copper. The calibration curve provides a high R²The value was 0.9998.

Figure 20 shows PEI concentrations for various TFs as determined at two different dilutions based on the calibration curve of figure 19. Figure 20 illustrates that different dilutions do not interfere with the readings.

Figure 21 shows PEI concentrations for various TFs as determined based on the calibration curve of figure 19 and in the presence and absence of copper (the latter used as a control test). As expected, the absorption strength of all samples was observed to be very low without the addition of Cu.

Figure 22 shows the correlation between the particle size of the printed image and the concentration of PEI in the TF used to create the image. FIG. 22 illustrates that there is a clear boundary between "good" (particle size 2.3 and below) and "bad" (particle size 2.3 and above). All "good samples" have a dark blue color (shown in grey scale in the figure), while other samples have different and other/lighter shades of blue (shown in grey scale in the figure).

Exemplary embodiments

The following embodiments are illustrative and are not intended to limit the claimed subject matter.

Embodiment 1a system for printing, comprising:

a replenishment reservoir configured to hold a second amount of the at least one depletable chemical, optionally in at least one liquid carrier,

Embodiment 2 the system of embodiment 1, wherein the detection tool is configured to measure and/or calculate the reduction.

Embodiment 3 the system of embodiment 1 or 2, wherein the detection tool is configured to record and/or report the reduction.

Embodiment 4 the system of any of embodiments 1-3, wherein the detection means is configured to activate the transfer means once the reduction has been identified.

Embodiment 5 the system according to any one of embodiments 1 to 4, wherein the system further comprises a control unit configured to control replenishment of the at least one depletable chemical agent in the liquid reservoir and optionally configured to activate the transfer means once the reduction has been identified.

Embodiment 6 the system of embodiment 5, wherein the system further comprises a communication means configured to transfer data/information between the detection means to the control unit.

Embodiment 7 the system of any one of embodiments 1 to 6, wherein the transfer tool is selected from a pressure-based tool, a jetting tool, a spraying tool, or a gravity tool.

Embodiment 8 the system of any of embodiments 1-7, wherein the system further comprises at least one printing liquid reservoir configured to hold a printing liquid, wherein the printing liquid is optionally an ink and more optionally a water-based ink.

Embodiment 9 the system of any one of embodiments 1 to 8, wherein the system is used for indirect printing.

Embodiment 10 the system of embodiment 9, wherein the system further comprises an intermediate transfer member.

Embodiment 11 the system of any of embodiments 8-10, wherein the formulation is a treatment formulation configured for application to and forming a coating on at least a region of the release surface of the intermediate transfer member.

Embodiment 12 the system of embodiment 11, wherein the formulation is applied to the release surface before the printing liquid is applied to the release surface.

Embodiment 13 the system of any one of embodiments 1 to 12, wherein the at least one depletable chemical agent is present in liquid form in the replenishment reservoir and wherein the replenishment reservoir and liquid reservoir are in liquid communication, thereby allowing transfer of at least a portion of the second amount of the at least one depletable chemical agent from the replenishment reservoir to the liquid reservoir once the reduction has been identified.

Embodiment 14 the system of embodiment 13, wherein the transfer means further comprises a regulating means configured to regulate the amount of transfer of the depletable chemical from the replenishment reservoir to the liquid reservoir and/or to avoid reverse flow of liquid from the liquid reservoir to the replenishment reservoir.

Embodiment 15 the system of embodiment 14, wherein the conditioning means comprises at least one safety valve allowing one-way flow of liquid from the refill reservoir to the liquid reservoir.

Embodiment 16 the system of any of embodiments 1-15, wherein the second amount of the at least one depletable chemical in the replenishment reservoir is greater than the first amount of the at least one depletable chemical in the liquid reservoir.

Embodiment 17 the system of any one of embodiments 1 to 16, wherein the system optionally further comprises a mixing tool configured to mix the at least one depletable chemical agent in the liquid reservoir and/or the replenishment reservoir.

Embodiment 18 the system of any one of embodiments 1 to 17, wherein the at least one depletable chemical in the replenishment reservoir is present in solid form.

Embodiment 19 the system of embodiment 18, wherein the system optionally further comprises a tool configured to mix, dissolve, or disperse the solid depletable chemical agent.

Embodiment 20 the system of embodiment 18 or 19, wherein the system optionally further comprises a heating means configured to assist in solubilizing the solid depletable chemical agent.

Embodiment 21 the system of any of embodiments 1-20, wherein after detecting/identifying the reduction, the control unit is configured to control replenishment of the at least one depletable chemical in the liquid reservoir to reach a value substantially equal to or greater than the predetermined threshold according to a replenishment profile selected to increase the amount of the depletable chemical in the liquid reservoir.

Embodiment 22 the system of any of embodiments 1-21, wherein the system further comprises a processing utility.

Embodiment 23 the system of embodiment 22, wherein the processing utility is configured to provide a signal indication to a user indicating a need to replenish the at least one depletable chemical agent in the liquid reservoir after the reduction is identified.

Embodiment 24 the system of any of embodiments 1-23, wherein the system optionally further comprises means for stopping the printing process and resuming the printing process once replenishment is achieved/completed.

Embodiment 25 the system of any one of embodiments 21 to 24, wherein the supplemental spectrum defines one or more of: an amount of the at least one depletable chemical to be transferred from the replenishment reservoir to the liquid reservoir; the frequency of the supplement; the duration of the transfer; the manner of the transfer; the transfer rate.

Embodiment 26 the system of any of embodiments 21-25, wherein the supplemental spectrum is determined based on one or more of: the first and/or second amount of the depletable chemical; the extent of said reduction; the relative amount of the depletable chemical relative to the amount of the formulation or the amount of the other component or components contained within the formulation.

Embodiment 27 the system of any one of embodiments 21 to 26, wherein the supplemental spectra are defined based on one or more of the printing conditions.

Embodiment 28 the system of any of embodiments 22-27, wherein the processing utility is configured to process images generated by the system and evaluate image print quality thereof, wherein the control unit is configured to cause replenishment of the at least one depletable chemical agent in the liquid reservoir when the image print quality is below a predetermined desired quality.

Embodiment 29 the system of embodiment 28, wherein the processing utility is configured to generate an output indicative of the quality of the image, wherein the control unit is configured to cause replenishment of the at least one depletable chemical agent in the liquid reservoir when the output is below a predetermined threshold parameter.

Embodiment 30 the system of embodiment 29, wherein the processing unit is configured to display the output on a visual display unit, an audio device, or a combination thereof.

Embodiment 31 the system of embodiment 29, wherein the predetermined threshold parameter comprises a substantially different value or range of values representative of a desired printed image quality.

Embodiment 32 the system of any of embodiments 29-31, wherein when the output is below a predetermined threshold parameter value, the system is optionally configured to immediately alert a user to stop or automatically stop the printing process, and optionally to resume the printing process once replenishment of the depletable chemical in the liquid reservoir is complete.

Embodiment 33 the system of any of embodiments 29 to 32, wherein the output reflects a value indicative of a granularity of the image.

Embodiment 34 the system of any of embodiments 1-33, further comprising a user interface.

Embodiment 35 the system of embodiment 34, wherein the user interface is configured to allow a user to introduce one or more desired printing conditions for a printing process into the processing utility.

Embodiment 37 the system of any of embodiments 1-35, further comprising a memory.

Embodiment 38 the system of embodiment 36, wherein the memory comprises a database of one or more image quality predetermined threshold parameters of a printing process.

Embodiment 39 the system of embodiment 36 or 37, wherein the processing utility is configured to correlate the image quality predetermined threshold parameter from the database with the output.

Embodiment 40 the system of any of embodiments 1-38, wherein the system further comprises a tool to record replenishment history.

Embodiment 41 the system of any one of embodiments 1 to 39, wherein the detection tool is selected from a visual tool, a spectroscopic tool, a spectrophotometric tool, an electronic tool, a chemical tool, a physical tool, a print quality based tool, or any combination thereof.

Embodiment 42 the system of embodiment 40, wherein the tool is configured to detect/measure the amount of the at least one depletable chemical in the liquid reservoir, and wherein the system is configured to calculate the reduction in the first amount of the at least one depletable chemical based on the detected/measured amount.

Embodiment 43 the system of any one of embodiments 1 to 41, wherein the system further comprises a sampling unit configured to withdraw an aliquot of the formulation from the liquid reservoir for further analysis.

Embodiment 44 the system of embodiment 42, wherein the sampling unit is configured to withdraw an aliquot of the formulation from the liquid reservoir as needed and/or at predetermined time intervals and/or after a predetermined number of print cycles.

Embodiment 45 the system of any one of embodiments 1 to 43, wherein the reduction of the first amount of the depletable chemical agent is relative to the amount of another component or components of the formulation.

Embodiment 46 the system of any of embodiments 1-44, wherein the reduction of the first amount of the depletable chemical occurs as a result of an undesirable side reaction of the depletable chemical.

Embodiment 47 the system of embodiment 45, wherein the undesirable side reaction of the depletable chemical agent results in the formation of an undesirable byproduct in the liquid reservoir, and wherein the system optionally further comprises a tool configured to remove the byproduct.

Embodiment 48 the system of embodiment 46, wherein the system further comprises means for detecting the formation and optionally measuring/determining the amount of said undesired by-products in said liquid reservoir.

Embodiment 49 the system of embodiment 47, wherein the system further comprises a tool configured to correlate the detected formation of the undesired byproduct with the reduction of the first amount of the depletable chemical agent.

Embodiment 50 the system of any one of embodiments 1-48, wherein the reduction of the first amount of the depletable chemical is due to contamination of the formulation in the liquid reservoir with at least one contaminant, and wherein formation of at least one undesirable byproduct is due to interaction between the at least one depletable chemical and at least one contaminant.

Embodiment 51 the system of any one of embodiments 1 to 49, wherein the system further comprises at least one printing liquid reservoir configured to hold a printing liquid, optionally the printing liquid is an ink formulation, and wherein the reduction of the first amount of the depletable chemical is due to printing liquid contamination in the liquid reservoir.

Embodiment 52 the system of embodiment 50, wherein the printing liquid is an ink and comprises at least one binder and at least one colorant, and wherein the reduction of the first amount of the depletable chemical is due to an undesirable side reaction of the depletable chemical with the at least one binder.

Embodiment 53 the system of any of embodiments 1-51, wherein the system further comprises a protection unit configured to protect the liquid reservoir from contamination, such as ink contamination.

Embodiment 54 the system of any of embodiments 1-52, wherein the system optionally further comprises a measuring means configured to measure the volume of the liquid in the liquid reservoir, wherein when the measured volume is below a predetermined minimum volume, the system is configured to instruct a user to refill the liquid reservoir with an additional amount of liquid formulation.

Embodiment 55 the system of any of embodiments 1-53, wherein the system optionally further comprises a measuring means configured to measure an amount (e.g., volume/liquid or weight/solid) of the depletable chemical in the replenishment reservoir, wherein when the measured amount is below a predetermined minimum amount, the control unit is configured to instruct a user to refill the replenishment reservoir with a further amount of the depletable chemical.

Embodiment 56 the system of any one of embodiments 1 to 54, wherein the depletable chemical agent is a polymer agent containing an amine nitrogen atom in a plurality of functional groups, which need not be identical and can be combined.

Embodiment 57 the system of embodiment 55, wherein the polymer has a relatively high charge density.

Embodiment 58 the system of embodiment 55 or 56, wherein the polymer has a molecular weight equal to or greater than 10,000 g/mole.

Embodiment 59 the system of any one of embodiments 1 to 57, wherein the depletable chemical is a polymeric agent having at least one of: (a) a positive charge density of at least 3meq/g of said agent and an average molecular weight of at least 5,000, (b) a positive charge density of at least 6meq/g of said agent and an average molecular weight of at least 1,000, (c) a nitrogen content of at least 1% by weight and an average molecular weight of at least 50,000, and (d) a nitrogen content of at least 18% by weight and an average molecular weight of at least 10,000.

Embodiment 60 the system of any one of embodiments 1 to 58, wherein the depletable chemical agent is a polymeric agent having a density of positive charges.

Embodiment 61 the system of embodiment 59, wherein the positive charge density is at least 0.5meq/g, at least 1meq/g, at least 2meq/g, at least 3meq/g, at least 4meq/g, at least 5meq/g,6meq/g, at least 7meq/g, at least 8meq/g, at least 9meq/g, at least 10meq/g, at least 11meq/g, at least 12meq/g, at least 13meq/g, at least 14meq/g, at least 15meq/g, at least 16meq/g, at least 17meq/g, at least 18meq/g, at least 19meq/g, or at least 20meq/g of the agent.

Embodiment 61 the system of any one of embodiments 1 to 60, wherein the depletable chemical agent is a polymeric agent having an average molecular weight of at least 500, at least 800, at least 1,000, at least 1,300, at least 1,700, at least 2,000, at least 2,500, at least 3,000, at least 3,500, at least 4,000, at least 4,500, at least 5,000, at least 10,000, at least 15,000, at least 20,000, at least 25,000, at least 50,000, at least 100,000, at least 150,000, at least 200,000, at least 250,000, at least 500,000, at least 750,000, at least 1,000,000, or at least 2,000,000.

Embodiment 62 the system of any one of embodiments 1 to 61, wherein the depletable chemical agent is a polymeric agent having an average molecular weight of at least 2,000, at least 10,000, or at least 25,000.

Embodiment 63 the system of any one of embodiments 1 to 62, wherein the depletable chemical agent comprises one or more nitrogen atoms that can be positively charged.

Embodiment 64 the system of embodiment 63, wherein the one or more nitrogen atoms comprise at least 1 wt.%, at least 1.4 wt.%, at least 2 wt.%, at least 5 wt.%, at least 8 wt.%, at least 10 wt.%, at least 15 wt.%, at least 18 wt.%, at least 20 wt.%, at least 24 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, or at least 50 wt.% of the depletable chemical agent.

Embodiment 65 the system of any one of embodiments 1 to 64, wherein the depletable chemical is a composition comprising poly (diallyldimethylammonium chloride)A polymeric agent of units.

Embodiment 66 the system of any one of embodiments 1 to 64, wherein the depletable chemical agent is a chemical comprising polyallylamineA polymeric agent of units.

Embodiment 67 the system of any one of embodiments 1 to 64, wherein the depletable chemical is a composition comprising poly (4-vinylpyridine)A polymeric agent of units.

Embodiment 68 the method of any one of embodiments 1 to 67, wherein the depletable chemical polymer agent is selected from the group consisting of: linear polyethylenimine, branched polyethylenimine, modified polyethylenimine, poly (diallyldimethylammonium chloride), poly (4-vinylpyridine), polyallylamine, vinylpyrrolidone-dimethylaminopropylmethacrylamide copolymer (Viviprint 131), vinylcaprolactam-dimethylaminopropylmethacrylamide hydroxyethyl methacrylate copolymer (Viviprint 200), vinylpyrrolidone and quaternized copolymer of dimethylaminoethyl methacrylate with diethyl sulfate (Viviprint 650), guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride.

Embodiment 69 the system of embodiment 68, wherein the depletable chemical polymer agent is Polyethyleneimine (PEI).

Embodiment 70 the system of any of embodiments 1-69, wherein the first amount of the depletable chemical polymer agent in the formulation in the liquid reservoir is equal to or less than about 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, or equal to or at least about 0.05 wt%, or sometimes at least about 0.01 wt%.

Embodiment 71 the system of any of embodiments 1-70, wherein the depletable chemical polymer agent is a polymer agent that is PEI and wherein the predetermined threshold is at least 0.01 wt.%, at least 0.05 wt.%, at least 0.10 wt.%, at least 0.15 wt.%, or at least 0.20 wt.%.

Embodiment 72 the system of any of embodiments 1-71, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein the first amount thereof in the liquid reservoir is at a concentration, by weight, of at most 6%, at most 5%, at most 4%, at most 3%, at most 2.5%, at most 2.0%.

Embodiment 73 the system of any one of embodiments 1 to 72, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein the first amount thereof in the liquid reservoir is a concentration by weight that is in a range of 0.01 to 1%, 0.01 to 0.8%, 0.01 to 0.7%, 0.01 to 0.6%, 0.01 to 0.5%, 0.2 to 0.7%, 0.2 to 0.6%, or 0.2 to 0.5%.

Embodiment 74 the system of any one of embodiments 1 to 73, wherein the at least one depletable chemical is PEI wherein the first amount thereof in the formulation in the liquid reservoir is 0.25 wt% and the second amount thereof in the replenishment reservoir is 25 wt% in water.

Embodiment 75 the system of embodiment 74, wherein when the first amount of the PEI in the liquid reservoir is reduced to below a predetermined threshold of 0.01 wt%, the system is configured to transfer a portion of the second amount of the PEI from the replenishment reservoir to the liquid reservoir, thereby replenishing the amount of the PEI in the liquid reservoir to a value equal to or above the predetermined threshold (0.01 wt%) or replenishing the amount of the PEI in the liquid reservoir to a value equal to the first amount (0.25 wt%).

Embodiment 76 the system of any of embodiments 1-75, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein its average molecular weight is at least 20,000, at least 50,000, at least 100,000, at least 200,000, at least 350,000, at least 500,000, at least 700,000, at least 750,000, and optionally at most 3,000,000, at most 2,500,000, or at most 2,000,000.

Embodiment 77 the system of any one of embodiments 1 to 76, wherein the depletable chemical agent is a polymeric agent that is PEI, and wherein the PEI is a surfactant, a wetting agent, an anchoring agent, or any combination thereof.

Embodiment 78 the system of any one of embodiments 1 to 77, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the charge density of the PEI polymer is in the range of 16-20meq/g material.

Embodiment 79 the system of any of embodiments 1 to 77, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the charge density of the PEI polymer is 8 meq/g.

Embodiment 80 the system of any one of embodiments 1 to 79, wherein the depletable chemical is silicone-functionalized PEI.

Embodiment 81 the system of any one of embodiments 1 to 80, wherein the depletable chemical agent is a quaternary ammonium compound.

Embodiment 82 the system of embodiment 81, wherein the quaternary ammonium compound is Larostat264A (BASF).

Embodiment 83 the system of embodiment 81, wherein the quaternary ammonium compound is Foamquat SAQ (linoleamidopropyl ethyl dimethyl ammonium ethyl sulfate 90).

Embodiment 84 the system of any of embodiments 1 to 83, wherein the depletable chemical agent is water dispersible.

Embodiment 85 the system of any one of embodiments 1 to 83, wherein the depletable chemical is water soluble.

Embodiment 86 the system of any one of embodiments 1 to 85, wherein the depletable chemical is a solid at room temperature.

Embodiment 87 the system of any of embodiments 51 to 86, wherein the at least one binder in the ink is an anionic binder.

Embodiment 88 the system of embodiment 87, wherein the anionic binder is an acrylic binder and/or a sulfonic acid binder.

Embodiment 89 the system of any of embodiments 51 to 88, wherein the at least one binder in the ink is a negatively charged organic polymeric resin.

Embodiment 90 the system of embodiment 89, wherein the negatively charged organic polymer resin has an average molecular weight of at least 8,000.

Embodiment 91 the system of embodiment 89 or 90, wherein the at least one binder in the ink is an acrylic polymer and/or an acrylic-styrene copolymer.

Embodiment 92 the system of any of embodiments 51-91, wherein the binder is Joncryl 538 BASF.

Embodiment 93 the system of any one of embodiments 51 to 92, wherein the depletable chemical is PEI, and wherein the reduction in the first amount of PEI is due to an undesired side reaction thereof with the at least one binder.

Embodiment 94 the system of any one of embodiments 1 to 93, wherein the system further comprises means for detecting, measuring or calculating the concentration of the depletable chemical in the formulation contained within the liquid reservoir and calculating therefrom the reduction in the first amount of the depletable chemical.

Embodiment 95 the system of embodiment 94, wherein the depletable chemical is PEI.

Embodiment 96 the system of embodiment 94, wherein said tool is a spectroscopic tool configured to detect said PEI based on the reaction of copper with said PEI.

Embodiment 97 the system of any of embodiments 1-96, wherein the printing system is an indirect printing system, the system further comprising:

i. an Intermediate Transfer Member (ITM) comprising a release layer surface;

a replenishment unit comprising a replenishment reservoir as disclosed herein.

An image forming station configured to apply a printing liquid to form an image on an aqueous treatment formulation formed on the intermediate transfer member;

v. a transfer station for transferring the image onto the printing substrate, for example by pressure contact between the ITM and the printing substrate.

Embodiment 98 the system of embodiment 97, wherein the printing liquid is an ink optionally applied by jetting, and the system further comprises:

Embodiment 99 the system of any of embodiments 11-98, wherein the treatment formulation comprises:

at least one water-soluble polymer;

an aqueous carrier liquid; and

optionally, one or more of the following: (a) at least one humectant; (b) at least one surfactant and (c) at least one wetting agent.

Embodiment 100 the system of embodiment 99, wherein the treatment formulation further comprises at least one wetting agent.

Embodiment 101 the system of embodiment 100, wherein the wetting agent is PEI.

Embodiment 102 the system of embodiment 99, wherein the water soluble polymer is at least one modified polysaccharide.

Embodiment 103 the system of embodiment 102, wherein the modified polysaccharide is selected from a cellulose derivative, a cellulose ether, a methylcellulose, a hydroxypropyl methylcellulose, or any combination thereof.

Embodiment 104 the system of embodiment 103, wherein the modified polysaccharide is hydroxypropyl methylcellulose.

Embodiment 105 the system of any one of embodiments 1 to 104, wherein the treatment formulation is as disclosed and exemplified herein.

Embodiment 106 a method for preventing or minimizing print defects in a printing process, wherein the print defects are associated with a reduction in a first amount of at least one depletable chemical agent contained within a liquid formulation (optionally in a liquid carrier), the method comprising:

Embodiment 107 the method of embodiment 106, wherein the second amount of the at least one depletable chemical is provided in liquid form.

Embodiment 108 the method of embodiment 106, wherein the second amount of the at least one depletable chemical agent is provided in solid form.

Embodiment 109 the method of any one of embodiments 106 to 108, wherein the method further comprises mixing the at least a portion of the second amount of the at least one exhaustible chemical agent in the liquid formulation.

Embodiment 110 the method of embodiment 108, further comprising dissolving or dispersing the solid depletable chemical agent in at least one liquid carrier (which may be the same or different from the liquid carrier of the liquid formulation).

Embodiment 111 the method of embodiment 110, further comprising heating the solid depletable chemical to aid in its dissolution.

Embodiment 112 the method of any one of embodiments 106 to 111, wherein the liquid formulation is configured to be applied to a substrate on which an image is to be printed, or to an intermediate transfer member in an indirect printing process.

Embodiment 113 the method of any one of embodiments 106 to 112, wherein the method further comprises:

i. providing an Intermediate Transfer Member (ITM);

providing a treatment formulation;

applying the treatment formulation onto the image receiving surface of the ITM to form a wet treatment layer;

at least partially drying the wet treated layer to form an at least partially dried treated layer;

v. applying a printing liquid onto the at least partially dried treatment layer to form an image;

transferring the image onto a printing substrate by pressurized contact between the surface of the ITM and the printing substrate.

Embodiment 114 the method of embodiment 113, wherein the printing liquid is an ink, optionally an aqueous ink and the method further comprises:

applying ink drops on the at least partially dried treatment layer to form an ink image; and

at least partially drying the wet ink image on the aqueous treatment layer to form a partially dried ink image film to be transferred to the printing substrate.

Embodiment 115 the method of any one of embodiments 106 to 114, wherein the adding of the second amount of at least a portion of the at least one exhaustible chemical agent is performed according to a predetermined replenishment spectrum selected for increasing the amount of the exhaustible chemical agent in the liquid formulation to reach a value substantially equal to or greater than a predetermined threshold.

Embodiment 116 the method of any one of embodiments 106 to 115, wherein the method further comprises identifying a decrease in the first amount of the at least one depletable chemical relative to the amount of at least one other component in the formulation and providing a signal indicative of a need to add the at least one depletable chemical to the liquid formulation to reestablish the first amount of the depletable chemical in the liquid formulation substantially equal to or greater than the predetermined threshold to counteract the decrease.

Embodiment 117 the method of embodiment 116, wherein the supplemental spectrum is a predetermined spectrum determined based on one or more of the printing conditions.

Embodiment 118 the method of any one of embodiments 106 to 117, wherein the method further comprises processing the image produced in the method and assessing the image print quality thereof, wherein when the image print quality is below a predetermined desired quality, the method comprises adding at least a portion of the second amount of the at least one depletable chemical agent to the liquid formulation.

Embodiment 119 the method of embodiment 118, wherein the method comprises generating an output indicative of the image quality, wherein when the output is below a predetermined threshold parameter, the method comprises adding the at least a portion of the second amount of the at least one exhaustible chemical to the liquid formulation.

Embodiment 120 the method of embodiment 119, wherein the method comprises displaying the output on a visual display unit, an audio device, or a combination thereof.

Embodiment 121 the method of embodiment 119 or 120, wherein the output reflects a value indicative of a granularity of the image.

Embodiment 122 the method of embodiment 119, wherein the predetermined threshold parameter comprises a substantially different value or range of values representative of a desired printed image quality.

Embodiment 123 the method of any one of embodiments 106-122, further comprising identifying whether the first amount of the at least one depletable chemical agent decreases below a predetermined threshold, wherein the identifying is accomplished by a detection tool selected from a visual tool, a spectroscopic tool, a spectrophotometric measuring tool, an electronic tool, a chemical tool, a physical tool, a print quality-based tool, or any combination thereof, and wherein the method further comprises calculating a decrease in the first amount of the at least one depletable chemical agent relative to an amount of another or more components in the formulation based on the identified decrease in the first amount of the at least one depletable chemical agent.

Embodiment 124 the method of any one of embodiments 106 to 123, further comprising sampling an aliquot of the liquid formulation for analysis.

Embodiment 125 the method of embodiment 124, wherein the sampling is performed as needed and/or at predetermined time intervals and/or after a predetermined number of print cycles.

Embodiment 126 the method of any one of embodiments 106 to 125, wherein the reduction of the first amount of the depletable chemical agent is relative to the amount of another component or components contained within the formulation.

Embodiment 127 the method of any one of embodiments 106 to 126, wherein the reduction of the first amount of the depletable chemical is due to an undesired side reaction of the depletable chemical.

Embodiment 128 the method of embodiment 127, wherein the undesirable side reaction of the depletable chemical agent results in the formation of an undesirable byproduct within the liquid formulation.

Embodiment 129 the method of embodiment 128, wherein the method further comprises detecting the formation of the undesired by-products in the liquid formulation and optionally measuring/determining the amount thereof.

Embodiment 130 the method of embodiment 129, wherein the method further comprises correlating the detected formation of the undesired byproduct with the reduction in the first amount of the depletable chemical.

Embodiment 131 the method of any one of embodiments 106-130, wherein the reduction of the first amount of the depletable chemical is due to contamination of the liquid formulation with at least one contaminant, and wherein formation of at least one undesirable byproduct is due to interaction between the at least one depletable chemical and the at least one contaminant.

Embodiment 132 the method of any of embodiments 106-131, wherein the reduction of the first amount of the depletable chemical is due to contamination of ink in the liquid formulation.

Embodiment 133 the method of embodiment 132, wherein the ink contamination is due to one or more of: ink spillage, ink splash and recovery processes for the treatment formulation.

Embodiment 134 the method of any of embodiments 114-133, wherein the ink comprises at least one binder and at least one colorant, and wherein the reduction of the first amount of the depletable chemical is due to an undesirable side reaction of the depletable chemical with the at least one binder.

Embodiment 135 the method of any one of embodiments 106 to 134, wherein the method further comprises protecting the liquid formulation from contamination.

Embodiment 136 the method of any one of embodiments 128 to 135, wherein the method further comprises removing the byproduct from the liquid formulation.

Embodiment 137 the method of any one of embodiments 106 to 136, wherein the method further comprises measuring the volume of the liquid formulation, wherein when the measured volume is below a predetermined minimum volume, the method further comprises refilling the liquid formulation with a liquid formulation to be substantially equal to or above the predetermined minimum volume.

Embodiment 138 the method of any one of embodiments 106 to 137, wherein the depletable chemical agent is a polymer agent containing an amine nitrogen atom in a plurality of functional groups, which need not be identical and can be combined.

Embodiment 139 the method of embodiment 138, wherein the polymer has a relatively high charge density.

Embodiment 140 the method of embodiment 138 or 139, wherein the molecular weight of the polymer is equal to or greater than 10,000 g/mole.

Embodiment 141 the method of any one of embodiments 106 to 140, wherein the depletable chemical is a polymeric agent having at least one of: (a) a positive charge density of at least 3meq/g of said agent and an average molecular weight of at least 5,000, (b) a positive charge density of at least 6meq/g of said agent and an average molecular weight of at least 1,000, (c) a nitrogen content of at least 1% by weight and an average molecular weight of at least 50,000, and (d) a nitrogen content of at least 18% by weight and an average molecular weight of at least 10,000.

Embodiment 142 the method of any one of embodiments 106 to 141, wherein the depletable chemical agent is a polymeric agent having a density of positive charges.

Embodiment 143 the method of embodiment 142, wherein the positive charge density is at least 0.5meq/g, at least 1meq/g, at least 2meq/g, at least 3meq/g, at least 4meq/g, at least 5meq/g,6meq/g, at least 7meq/g, at least 8meq/g, at least 9meq/g, at least 10meq/g, at least 11meq/g, at least 12meq/g, at least 13meq/g, at least 14meq/g, at least 15meq/g, at least 16meq/g, at least 17meq/g, at least 18meq/g, at least 19meq/g, or at least 20meq/g of the agent.

Embodiment 144 the method of any one of embodiments 106 to 143, wherein the depletable chemical agent is a polymeric agent having an average molecular weight of at least 500, at least 800, at least 1,000, at least 1,300, at least 1,700, at least 2,000, at least 2,500, at least 3,000, at least 3,500, at least 4,000, at least 4,500, at least 5,000, at least 10,000, at least 15,000, at least 20,000, at least 25,000, at least 50,000, at least 100,000, at least 150,000, at least 200,000, at least 250,000, at least 500,000, at least 750,000, at least 1,000,000, or at least 2,000,000.

Embodiment 145 the method of any one of embodiments 106 to 144, wherein the depletable chemical agent is a polymeric agent having an average molecular weight of at least 2,000, at least 10,000, or at least 25,000.

Embodiment 146 the method of any one of embodiments 106 to 145, wherein the depletable chemical agent comprises one or more nitrogen atoms that can be positively charged.

Embodiment 147 the method of embodiment 146, wherein the one or more nitrogen atoms comprise at least 1 wt.%, at least 1.4 wt.%, at least 2 wt.%, at least 5 wt.%, at least 8 wt.%, at least 10 wt.%, at least 15 wt.%, at least 18 wt.%, at least 20 wt.%, at least 24 wt.%, at least 30 wt.%, at least 35 wt.%, at least 40 wt.%, at least 45 wt.%, or at least 50 wt.% of the depletable chemical agent.

Embodiment 148 the method of any of embodiments 106 to 147, wherein the depletable chemical is a composition comprising poly (diallyldimethylammonium chloride)A polymeric agent of units.

Embodiment 149 the method of any one of embodiments 106 to 147, wherein the depletable chemical agent is a chemical comprising polyallylamineA polymeric agent of units.

Embodiment 150 the method of any one of embodiments 106 to 147, wherein the depletable chemical agent is a composition comprising poly (4-vinylpyridine)A polymeric agent of units.

Embodiment 151 the method of any one of embodiments 106 to 147, wherein the depletable chemical polymer agent is selected from the group consisting of: linear polyethylenimine, branched polyethylenimine, modified polyethylenimine, poly (diallyldimethylammonium chloride), poly (4-vinylpyridine), polyallylamine, vinylpyrrolidone-dimethylaminopropylmethacrylamide copolymer (Viviprint 131), vinylcaprolactam-dimethylaminopropylmethacrylamide hydroxyethyl methacrylate copolymer (Viviprint 200), vinylpyrrolidone and quaternized copolymer of dimethylaminoethyl methacrylate with diethyl sulfate (Viviprint 650), guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride.

Embodiment 152 the method of embodiment 151, wherein the depletable chemical polymer agent is Polyethyleneimine (PEI).

Embodiment 153 the method of any one of embodiments 106 to 152, wherein the first amount of the depletable chemical polymer agent in the formulation in the liquid receptacle is equal to or less than about 5, 4,3, 2, 1, 0.5, 0.4, 0.3, 0.2, 0.1, or equal to or at least about 0.05 or sometimes at least about 0.01 weight percent.

Embodiment 154 the method of any one of embodiments 106 to 153, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein the predetermined threshold is at least 0.01 wt.%, at least 0.05 wt.%, at least 0.10 wt.%, at least 0.15 wt.%, or at least 0.20 wt.%.

Embodiment 155 the method of any one of embodiments 106 to 154, wherein the depletable chemical agent is a polymeric agent that is PEI, and wherein the first amount thereof by weight in the liquid formulation is at most 6%, at most 5%, at most 4%, at most 3%, at most 2.5%, at most 2.0%.

Embodiment 156 the method of any one of embodiments 106 to 155, wherein the depletable chemical is a polymeric agent that is PEI, and wherein the first amount thereof by weight in the liquid formulation is in the range of 0.01 to 1%, 0.01 to 0.8%, 0.01 to 0.7%, 0.01 to 0.6%, 0.01 to 0.5%, 0.2 to 0.7%, 0.2 to 0.6%, or 0.2 to 0.5%.

Embodiment 157 the method of any one of embodiments 106 to 156, wherein the at least one depletable chemical is PEI wherein the first amount thereof in the formulation in the liquid reservoir is 0.25 wt% and the second amount thereof in the replenishment reservoir is 25 wt% in water.

Embodiment 158 the method of embodiment 157, wherein when said first amount of said PEI in said liquid formulation is reduced to below a predetermined threshold of 0.01 wt%, adding a portion of said second amount of said PEI to said liquid formulation, thereby supplementing the amount of said PEI in said liquid formulation to a value at or above said predetermined threshold (0.01 wt%), or supplementing the amount of said PEI in said liquid formulation to a value at said first amount (0.25 wt%).

Embodiment 159 the method of any one of embodiments 106 to 158, wherein the depletable chemical agent is a polymeric agent that is PEI and wherein its average molecular weight is at least 20,000, at least 50,000, at least 100,000, at least 200,000, at least 350,000, at least 500,000, at least 700,000, at least 750,000, and optionally at most 3,000,000, at most 2,500,000, or at most 2,000,000.

Embodiment 160 the method of any one of embodiments 106 to 159, wherein the depletable chemical agent is a polymeric agent that is PEI, and wherein the PEI is a surfactant, a wetting agent, an anchoring agent, or any combination thereof.

Embodiment 161 the method of any one of embodiments 106 to 160, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the PEI polymer has a charge density in the range of 16-20meq/g material.

Embodiment 162 the method of any one of embodiments 106 to 160, wherein the depletable chemical agent is a polymer agent that is PEI, wherein the charge density of the PEI polymer is 8 meq/g.

Embodiment 163 the method of any one of embodiments 106 to 162, wherein the depletable chemical is silicone-functionalized PEI.

Embodiment 164 the method according to any one of embodiments 106 to 163, wherein the depletable chemical agent is a quaternary ammonium compound.

Embodiment 165 the method of embodiment 164, wherein the quaternary ammonium compound is Larostat264A (BASF).

Embodiment 166 the method of embodiment 164, wherein the quaternary ammonium compound is Foamquat SAQ (linoleamidopropyl ethyl dimethyl ammonium ethyl sulfate 90).

Embodiment 167 the method of any one of embodiments 106 to 166, wherein the depletable chemical agent is water dispersible.

Embodiment 168 the method of any one of embodiments 106 to 166, wherein the depletable chemical agent is water soluble.

Embodiment 169 the method of any one of embodiments 106 to 168, wherein the depletable chemical is a solid at room temperature.

Embodiment 170 the method of any one of embodiments 134 to 169, wherein the at least one binder in the ink formulation is a negatively charged organic polymer resin.

Embodiment 171 the method of embodiment 170, wherein the negatively charged organic polymer resin has an average molecular weight of at least 8,000.

Embodiment 172 the method of embodiment 170 or 171, wherein the at least one binder in the ink formulation is an acrylic polymer and/or an acrylic-styrene copolymer.

Embodiment 173 the method of embodiment 170, wherein the binder is Joncryl 538 BASF.

Embodiment 174 the method of any one of embodiments 106 to 173, wherein the depletable chemical agent is PEI, and wherein the reduction in the first amount of PEI is due to an undesired side reaction thereof with the at least one binder.

Embodiment 175 the method of any one of embodiments 106 to 174, wherein the method further comprises detecting and/or measuring and/or calculating the concentration of the depletable chemical in the liquid formulation and calculating therefrom the reduction in the first amount of the depletable chemical.

Embodiment 176 the method of embodiment 175, wherein the depletable chemical agent is PEI and wherein the detecting and/or measuring and/or calculating is by spectroscopic means using the reaction of copper with the PEI.

Embodiment 177 the method of any one of embodiments 106 to 176, wherein the treatment formulation comprises:

at least one water-soluble polymer;

an aqueous carrier liquid; and

optionally, one or more of the following: (a) at least one humectant; (b) at least one surfactant and (c) at least one wetting agent.

Embodiment 178 the method of embodiment 177, wherein the treatment formulation further comprises at least one wetting agent.

Embodiment 179 the method of embodiment 178, wherein the wetting agent is PEI.

Embodiment 180 the method of embodiment 177, wherein the water soluble polymer is at least one modified polysaccharide.

Embodiment 181 the method of embodiment 180, wherein the modified polysaccharide is selected from a cellulose derivative, a cellulose ether, a methylcellulose, a hydroxypropyl methylcellulose, or any combination thereof.

Embodiment 182 the method of embodiment 181, wherein the modified polysaccharide is hydroxypropyl methylcellulose.

Embodiment 183 the method according to any one of embodiments 1 to 182, wherein the treatment formulation is as disclosed and exemplified herein.

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System and method for preventing or minimizing print defects in a printing process

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