阅读说明：本技术 白色喷墨墨组合物、墨涂覆方法和经涂覆的制品 (White ink jet ink composition, ink coating method, and coated article ) 是由 陈玟铮 黄贯豪 R-M·黄 于 2018-06-27 设计创作，主要内容包括：一种白色喷墨墨组合物、喷墨墨涂覆方法和所得到的喷墨涂覆的制品全都基于如下白色喷墨墨组合物,其包括：颗粒颜料材料、树脂组合物和溶剂组合物。在热固化之后,未固化的树脂组合物形成固化的树脂组合物,其与基材(例如但不限于玻璃基材、玻璃陶瓷基材、陶瓷基材、金属氧化物基材、金属基材和聚合物基材)粘附。(A white inkjet ink composition, an inkjet ink coating method and the resulting inkjet coated article are all based on a white inkjet ink composition comprising: a particulate pigment material, a resin composition and a solvent composition. After thermal curing, the uncured resin composition forms a cured resin composition that adheres to a substrate (such as, but not limited to, a glass substrate, a glass ceramic substrate, a metal oxide substrate, a metal substrate, and a polymer substrate).)

1. An ink composition comprising:

a white pigment material;

a resin composition comprising:

a silicone resin component; and

at least one of an amino resin component or an acrylic resin component; and

a solvent composition comprising one or more of: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or diethylene glycol diethyl ether.

2. The ink composition of claim 1, wherein the ink composition is ink jet printable and thermally curable.

3. The ink composition of claim 1 or 2, wherein the white pigment material comprises titanium dioxide powder having an average particle size D50 of 100nm to 250 nm.

4. The ink composition of claim 3, wherein the average particle size D50 is 150nm to 250 nm.

5. The ink composition of any preceding claim, wherein the silicone resin component comprises a silsesquioxane.

6. The ink composition of claim 5, wherein the silsesquioxane is divinylhexamethyloctasilsesquioxane.

7. The ink composition of any preceding claim, wherein the solvent composition comprises two or more of: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or diethylene glycol diethyl ether.

8. The ink composition of any preceding claim, wherein the solvent composition comprises three or more of: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or diethylene glycol diethyl ether.

9. The ink composition of any preceding claim, wherein the solvent composition comprises: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate and diethylene glycol diethyl ether.

10. An ink composition as claimed in any preceding claim, wherein the propylene glycol ether is propylene glycol monomethyl ether.

11. The ink composition of any preceding claim, further comprising:

a dispersant; and

a flow promoter.

12. The ink composition of claim 11, wherein the flow promoter comprises a modified polyether polydimethylsiloxane.

13. An ink composition as claimed in any preceding claim, wherein the resin composition comprises an amino resin component and an acrylic resin component.

14. An ink composition as claimed in any preceding claim, wherein the resin composition further comprises an epoxy resin component.

15. The ink composition of any preceding claim, comprising:

a pigment material in the range of 9 to 14 weight percent;

a silicone resin component in the range of 12 to 25 weight percent;

an amino resin component in the range of 0 to 10 weight percent;

an acrylic resin component in the range of 0 to 10 weight percent;

propylene glycol ether in the range of 15 to 25 wt%;

diethylene glycol dimethyl ether in the range of 10 to 20 wt%;

diethylene glycol diethyl ether in the range of 0 to 10 wt%; and

propylene glycol methyl ether acetate in the range of 13 to 25 wt%.

16. The ink composition of claim 15, further comprising:

a dispersant in the range of 1 to 4 wt%;

a flow promoter in the range of 0.5 to 3.5 wt%; and

an epoxy resin component in the range of 0 to 10 weight percent.

17. An ink coating method comprising the steps of:

coating an uncured inkjet ink composition according to any preceding claim on a substrate; and

the uncured inkjet ink composition is cured in situ, forming a cured ink composition on the substrate.

18. The method of claim 17, wherein the substrate is selected from the group consisting of: glass substrates, glass ceramic substrates, metal oxide substrates, metal substrates, and polymeric substrates.

19. The method of claim 17 or 18, wherein the uncured inkjet ink composition is thermally cured to form a cured ink composition.

20. The method of any of claims 17-19, wherein the optical density of the cured ink composition ranges from greater than 0.2 to 1.0.

21. The method of claim 20, wherein the optical density of the cured ink composition ranges from greater than 0.5 to 1.0.

22. A coated article, the coated article comprising:

a substrate; and

a cured coating on a substrate, the cured coating comprising the ink composition of any one of claims 1-16.

23. The coated article of claim 22, wherein the cured coating has a thickness of 1 to 10 microns.

24. The coated article of claim 22 or 23, wherein the cured coating has an optical density in the range of greater than 0.2 to 1.0.

25. The coated article of claim 24, wherein the cured coating has an optical density in the range of greater than 0.5 to 1.0.

26. The coated article of any of claims 22-25, wherein the cured coating adheres to the substrate greater than or equal to 4B according to the cross-hatch adhesion test of ASTM D3359-09e 2.

27. An electronic device comprising the coated article of any one of claims 22-26.

Technical Field

The present disclosure relates generally to inkjet ink compositions, inkjet printed articles, and inkjet printing methods.

Background

Ink jet ink compositions for use in ink jet ink printing processes are well known materials that often provide accurate and repeatable images on porous substrates such as paper substrates. Unfortunately, ink image adhesion and opacity are often compromised when used on low porosity substrates such as glass substrates. For example, adhesion problems of ink to a less porous substrate (e.g., glass) can result in poor color density and image clarity, particularly for colored inks.

Accordingly, there is a need in the art for an ink jet ink composition and printing method that provides enhanced glass substrate adhesion properties and enhanced opacity properties.

Disclosure of Invention

The present disclosure relates to ink jet ink compositions and printing methods that provide enhanced substrate adhesion properties and enhanced opacity (e.g., optical density). Embodiments described herein or contemplated herein relate to an ink jet ink composition having a pigment component, a resin composition, and a solvent composition that provides a cured ink jet ink composition having enhanced adhesion and increased opacity relative to a substrate surface, particularly where the substrate surface comprises a glass surface, a ceramic surface, a metal oxide surface, a metal surface, a polymeric surface, or the like. Similarly, embodiments described or contemplated herein relate to inkjet printing an ink composition having a pigment component, a resin composition, and a solvent composition onto a substrate surface (e.g., a glass surface, a ceramic surface, a metal oxide surface, a metal surface, a polymer surface, or the like).

In aspect (1), the disclosed ink composition comprises:

a white pigment material;

a resin composition comprising:

a silicone resin component; and

at least one of an amino resin component or an acrylic resin component; and

a solvent composition comprising one or more of: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or diethylene glycol diethyl ether.

Aspect (2) according to aspect (1), wherein the ink composition is ink jet printable and thermally curable.

Aspect (3) according to aspect (1) or (2), wherein the white pigment material comprises a titanium dioxide powder having an average particle size D50 of 100nm to 250 nm.

Aspect (4) according to aspect (3), wherein the average particle size D50 is 150nm to 250 nm.

Aspect (5) according to any preceding aspect, wherein the silicone resin component comprises a silsesquioxane.

Aspect (6) according to aspect (5), wherein the silsesquioxane is divinylhexamethyloctasilsesquioxane.

Aspect (7) according to any preceding aspect, wherein the solvent composition comprises two or more of: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or diethylene glycol diethyl ether.

Aspect (8) according to any preceding aspect, wherein the solvent composition comprises three or more of: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or diethylene glycol diethyl ether.

Aspect (9) according to any preceding aspect, wherein the solvent composition comprises: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate and diethylene glycol diethyl ether.

The aspect (10) according to any preceding aspect, wherein the propylene glycol ether is propylene glycol monomethyl ether.

Aspect (11) according to any preceding aspect, further comprising a dispersant and a flow promoter.

Aspect (12) according to aspect (11), wherein the flow promoter comprises a modified polyether polydimethylsiloxane.

Aspect (13) according to any preceding aspect, wherein the resin component comprises an amino resin component and an acrylic resin component.

The aspect (14) according to any preceding aspect, wherein the resin component further comprises an epoxy resin component.

An aspect (15) according to any preceding aspect, comprising:

a pigment material in the range of 9 to 14 weight percent;

a silicone resin component in the range of 12 to 25 weight percent;

an amino resin component in the range of 0 to 10 weight percent;

an acrylic resin component in the range of 0 to 10 weight percent;

propylene glycol ether in the range of 15 to 25 wt%;

diethylene glycol dimethyl ether in the range of 10 to 20 wt%;

diethylene glycol diethyl ether in the range of 0 to 10 wt%; and

propylene glycol methyl ether acetate in the range of 13 to 25 wt%.

The aspect (16) according to aspect (15), further comprising:

a dispersant in the range of 1 to 4 wt%;

a flow promoter in the range of 0.5 to 3.5 wt%; and

an epoxy resin component in the range of 0 to 10 weight percent.

In the aspect (17), the ink coating method includes the steps of:

coating an uncured inkjet ink composition of any of the preceding aspects on a substrate; and curing the uncured inkjet ink composition in situ to form a cured ink composition on the substrate.

Aspect (18) according to aspect (17), wherein the substrate is selected from the group consisting of: glass substrates, glass ceramic substrates, metal oxide substrates, metal substrates, and polymeric substrates.

Aspect (19) according to aspect (17) or (18), wherein the uncured inkjet ink composition is thermally cured to form a cured ink composition.

Aspect (20) according to any one of aspects (17) to (19), wherein the optical density of the cured ink composition ranges from greater than 0.2 to 1.0.

Aspect (21) according to aspect (20), wherein the optical density of the cured ink composition ranges from greater than 0.5 to 1.0.

In aspect (22), the coated article comprises: a substrate; and a cured coating on the substrate, the cured coating comprising the ink composition of any one of aspects (1) to (16).

Aspect (23) according to aspect (22), wherein the cured coating has a thickness in a range of 1 micron to 10 microns.

Aspect (24) according to aspect (22) or (23), wherein the cured coating has an optical density in a range of greater than 0.2 to 1.0.

Aspect (25) according to aspect (24), wherein the cured coating has an optical density in a range of greater than 0.5 to 1.0.

Aspect (26) according to any one of aspects (22) - (25), wherein the cured coating adheres to the substrate greater than or equal to 4B according to the cross-hatch adhesion test of ASTM D3359-09e 2.

In aspect (27), the consumer electronic device comprises the coated article of any one of aspects (22) - (26).

These and other aspects of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.

Drawings

Objects, features and advantages of the embodiments herein will be understood from the detailed description set forth below. The detailed description is to be understood in light of the accompanying figures, in which like reference numerals generally refer to like parts throughout the different views. Moreover, the drawings are not necessarily to scale, emphasis instead generally being placed upon illustrating the principles of the invention.

Figure 1 is a schematic diagram of the chemical structure of a divinylhexamethyloctasilsesquioxane resin component according to some embodiments.

FIG. 2 is a thermal desorption gas chromatography mass spectrometry (GC/MS) graph of a divinylhexamethyloctasilsesquioxane resin component according to some embodiments.

Detailed Description

Embodiments described herein or contemplated herein relate to white inkjet ink compositions and printing methods that provide enhanced substrate adhesion properties and enhanced opacity properties (e.g., optical density). According to various embodiments, an inkjet ink composition includes a pigment component, a resin composition, and a solvent composition, which provides a cured inkjet ink composition having enhanced adhesion and increased opacity relative to a substrate surface, particularly where the substrate surface includes a glass surface, a glass-ceramic surface, a metal oxide surface, a metal surface, a polymer surface, or the like. According to various embodiments, the inkjet printing method described herein employs a series of steps as follows: the ink composition having the pigment component, the resin composition, and the solvent composition is ink-jetted onto a substrate surface (e.g., a glass surface, a glass-ceramic surface, a metal oxide surface, a metal surface, a polymer surface, or the like). In some embodiments, the white inkjet ink composition has a suitable viscosity (e.g., 2 to 6 centipoise) and a suitable average particle size D50 (e.g., 100 to 250nm) for the pigment material, such that the white inkjet ink composition is inkjet printable. In some embodiments, the white ink jet ink composition is thermally curable.

Inkjet printing also provides the ability to print on 3D or 2.5D shaped substrates, which is not easily or easily achievable by other printing techniques (e.g., screen printing). Screen printing relies on the use of a screen to apply ink to a substrate by squeezing the ink through openings in the screen by a squeegee (squeegee). The screen needs to be in full contact with the substrate in order to perform the screen printing process, which results in limited or no capacity for some 3D and 2.5D shaped substrates. On the other hand, ink jet printing does not require the print head to contact the substrate, but rather, the print head is perpendicular to the substrate surface. A 3D shaped substrate includes a substrate wherein both major surfaces of the substrate have curvature, for example at one or more edges of the substrate. 2.5D-shaped substrates include substrates in which only one major surface of the substrate has curvature, for example at one or more edges of the substrate. In some embodiments, the substrate may have 4 edges, and the substrate may have curvature at 1,2, 3, or all 4 edges. In some embodiments, the ink compositions disclosed herein are compatible with inkjet printing on 3D shaped and 2.5D shaped substrates.

In some embodiments, an ink jet ink composition comprises: a white pigment material; a resin composition comprising: a silicone resin component; and at least one of an amino resin component or an acrylic resin component; and a solvent composition comprising one or more of: propylene glycol ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate or diethylene glycol diethyl ether.

Ink jet ink composition

According to some embodiments, the uncured inkjet ink composition comprises a pigment material, which may include, but is not limited to, a white pigment material. In some embodiments, the white pigment material is titanium dioxide (TiO)₂) And (3) powder. In some embodiments, the pigment material has a suitable average particle size D50 to enable inkjet printing of the uncured inkjet ink composition with reduced or minimized inkjet printhead clogging. In some embodiments, the average particle size D50 of the titanium dioxide powder is in the following range: 100nm to 250nm, 100nm to 225nm, 100nm to 200nm, 100nm to 175nm, 100nm to 150nm, 100nm to 125nm, 125nm to 250nm, 125nm to 225nm, 125nm to 200nm, 125nm to 175nm, 125nm to150nm, 150nm to 250nm, 150nm to 225nm, 150nm to 200nm, 150nm to 175nm, 175nm to 250nm, 175nm to 225nm, 175nm to 200nm, 200nm to 250nm, 200nm to 225nm, 225nm to 250nm, or any range and subrange therebetween. The average particle size D50 was measured by a Microtrac nano Wave W3205 scale. For the measurement, the ink was diluted to a 1:100 ratio and poured into a gauge chamber. The vector table inputs the reflectance of the pigment material. During operation of the meter, the wavelength of the light source passing through the dilute solution was collected and the wavelength data was then correlated to the D50 particle size. In some embodiments, the titanium dioxide powder may be milled by conventional techniques to achieve the desired average particle size D50. In some embodiments, the uncured inkjet ink composition comprises the following amounts of white pigment material: 9 to 14 weight percent, 9 to 13 weight percent, 9 to 12 weight percent, 9 to 11 weight percent, 9 to 10 weight percent, 10 to 14 weight percent, 10 to 13 weight percent, 10 to 12 weight percent, 10 to 11 weight percent, 11 to 14 weight percent, 11 to 13 weight percent, 11 to 12 weight percent, 12 to 14 weight percent, 12 to 13 weight percent, 13 to 14 weight percent, or any range or subrange therebetween. In some embodiments, the white pigment material provides the ink with a white color, allows the ink to achieve a suitable optical density after inkjet printing onto a substrate, and is one factor in maintaining a suitable resistance of the ink after printing and curing. In some embodiments, pigments for use in the uncured inkjet ink composition are commercially available.

An uncured inkjet ink composition according to various embodiments includes an uncured resin composition. The uncured resin composition of the uncured inkjet ink composition ensures adhesion of the particulate pigment material component to the substrate (i.e., particularly, glass substrate) and is capable of encasing the pigment material to prevent solidification of the pigment material. In addition, the uncured resin composition of the uncured inkjet ink composition helps to meet or pass environmental reliability test standards for the particular end use application of the inkjet ink coated and cured substrate when cured. According to some embodiments, the uncured resin composition of the uncured inkjet ink composition may also ensure and provide additional functional attributes of the cured inkjet ink composition coated article when cured, such as, but not limited to: solvent and chemical resistance and desired electrical resistance characteristics.

In some embodiments, the uncured inkjet ink composition comprises an uncured resin composition in the range of: 25 to 32 weight percent, 25 to 31 weight percent, 25 to 30 weight percent, 25 to 29 weight percent, 25 to 28 weight percent, 25 to 27 weight percent, 25 to 26 weight percent, 26 to 32 weight percent, 26 to 31 weight percent, 26 to 30 weight percent, 26 to 29 weight percent, 26 to 28 weight percent, 26 to 27 weight percent, 27 to 32 weight percent, 27 to 31 weight percent, 27 to 30 weight percent, 27 to 29 weight percent, 27 to 28 weight percent, 28 to 32 weight percent, 28 to 31 weight percent, 28 to 30 weight percent, 28 to 29 weight percent, 29 to 32 weight percent, 29 to 31 weight percent, 29 to 30 weight percent, 30 to 32 weight percent, 30 to 31 weight percent, 31 to 32 weight percent, or any range or subrange therebetween.

In some embodiments, the uncured resin composition includes, but is not necessarily limited to, an uncured silicone resin component. In some embodiments, the uncured inkjet ink composition comprises an uncured silicone resin component in the following ranges: 12 to 25 weight percent, 12 to 22 weight percent, 12 to 20 weight percent, 12 to 18 weight percent, 12 to 15 weight percent, 15 to 25 weight percent, 15 to 22 weight percent, 15 to 20 weight percent, 15 to 18 weight percent, 18 to 25 weight percent, 18 to 22 weight percent, 18 to 20 weight percent, 20 to 25 weight percent, 20 to 22 weight percent, 22 to 25 weight percent, or any range or subrange therebetween.

According to embodiments, the uncured silicone resin component in the uncured inkjet ink composition includes and may alternatively be defined as a silsesquioxane uncured silicone resin component and is, for example (but not limited to), a divinylhexamethyloctasilsesquioxane uncured silicone resin component (Vin)₂Me₆Si₈) The chemical structure is shown in figure 1. FIG. 2 is a thermal desorption gas chromatography mass spectrum of divinylhexamethyloctasilsesquioxane uncured silicone resin component.

Vin, as understood by those skilled in the art₂Me₆Si₈The chemical structure of the silsesquioxane uncured silicone resin component is shown in fig. 1, which is a condensation product of two molecules of a vinyl tri-substitutable silane and six molecules of a methyl tri-substitutable silane. The aforementioned trisubstituted portions of the vinylsilane and methylsilane molecules may include (for example, but are not limited to): substitutable chemical functional groups include, but are not limited to, suitable halide functional groups and suitable alkoxide functional groups. Thus, suitable silane starting materials that may be used to prepare the silsesquioxane uncured silicone resin component having the chemical structure shown in fig. 1 may include, but are not limited to: vinyl-triethoxysilane, and methyl-trimethoxysilane. According to some embodiments, the silsesquioxane uncured silicone resin component having a chemical structure as shown in fig. 1 comprises about 12 to 25 wt% of the uncured inkjet ink composition. The silsesquioxane uncured silicone resin component having the chemical structure shown in fig. 1 is also characterized as a transparent viscous fluid having from about 30% to about 45% solids, a viscosity of from about 10 to about 20 centipoise at 25 ℃, and from about 0.9 to about 1.0 g/cm at 23 ℃³And a surface tension of about 26 to 29 dynes/cm.

According to some embodiments, a suitable uncured silicone resin component for use in an uncured resin composition in an uncured inkjet ink composition (i.e., including, but not limited to, Vin having a chemical structure as shown in fig. 1)₂Me₆Si₈Silsesquioxane) is commercially available from any of several commercial sources as the appropriately designated uncured silicone resin. As noted above, the uncured silicone resin component may alternatively be prepared by the in situ reaction of a suitable vinylsilane with a suitable methylsilane in a ratio of 1: 3.

In some embodiments, the uncured resin composition may include, in addition to the uncured silicone resin component, one or more of the following: an uncured amino resin component, an uncured acrylic resin component, and an uncured epoxy resin component. In some embodiments, the uncured inkjet ink composition comprises an uncured acrylic resin component in the range of: 0 to 10 weight percent, 0 to 8 weight percent, 0 to 6 weight percent, 0 to 4 weight percent, greater than 0 to 10 weight percent, greater than 0 to 8 weight percent, greater than 0 to 6 weight percent, greater than 0 to 4 weight percent, 2 to 10 weight percent, 2 to 8 weight percent, 2 to 6 weight percent, 2 to 4 weight percent, 4 to 10 weight percent, 4 to 8 weight percent, 4 to 6 weight percent, 6 to 10 weight percent, 6 to 8 weight percent, 8 to 10 weight percent, or any range or subrange therebetween. In some embodiments, the uncured inkjet ink composition comprises an uncured amino resin component in the range of: 0 to 10 weight percent, 0 to 8 weight percent, 0 to 6 weight percent, 0 to 4 weight percent, greater than 0 to 10 weight percent, greater than 0 to 8 weight percent, greater than 0 to 6 weight percent, greater than 0 to 4 weight percent, 2 to 10 weight percent, 2 to 8 weight percent, 2 to 6 weight percent, 2 to 4 weight percent, 4 to 10 weight percent, 4 to 8 weight percent, 4 to 6 weight percent, 6 to 10 weight percent, 6 to 8 weight percent, 8 to 10 weight percent, or any range or subrange therebetween. In some embodiments, the uncured inkjet ink composition comprises an uncured epoxy resin component in the range of: 0 to 10 weight percent, 0 to 8 weight percent, 0 to 6 weight percent, 0 to 4 weight percent, greater than 0 to 10 weight percent, greater than 0 to 8 weight percent, greater than 0 to 6 weight percent, greater than 0 to 4 weight percent, 2 to 10 weight percent, 2 to 8 weight percent, 2 to 6 weight percent, 2 to 4 weight percent, 4 to 10 weight percent, 4 to 8 weight percent, 4 to 6 weight percent, 6 to 10 weight percent, 6 to 8 weight percent, 8 to 10 weight percent, or any range or subrange therebetween. In some embodiments, the uncured amino resin component, the uncured acrylic resin component, and the uncured epoxy resin component used in the uncured inkjet ink composition are commercially available.

An uncured inkjet ink composition according to various embodiments includes a solvent composition. Generally, according to various embodiments, the solvent material is selected to act as a carrier for the pigment material particles to achieve uniform and smooth ejection of the pigment material particles from the ink jet print head onto a non-porous substrate, such as, but not limited to, a glass substrate, a glass ceramic substrate, a metal oxide substrate, a metal substrate, and/or a polymer substrate. In addition, the solvent component is selected to control the drying, fluid, and wetting properties of the uncured inkjet ink composition, and to ensure that the viscosity and surface tension of the uncured inkjet ink composition do not change with temperature, thereby maintaining stable printing performance (e.g., the inkjet head nozzles do not clog frequently). The solvent composition also adjusts the viscosity of the ink to balance having a volatility low enough to remain stable during storage and use so that drying or clogging of the inkjet printhead nozzles does not occur, and a volatility high enough to minimize or prevent excessive flow and de-wetting of the ink after inkjet printing onto a substrate. Further, it is contemplated that the solvent composition in the uncured inkjet ink composition according to embodiments may be characterized at 200 ℃ using gas chromatography analysis.

In some embodiments, the uncured inkjet ink composition comprises a solvent composition in the range of: 50 to 60 wt%, 50 to 59 wt%, 50 to 58 wt%, 50 to 57 wt%, 50 to 56 wt%, 50 to 55 wt%, 50 to 54 wt%, 50 to 53 wt%, 50 to 52 wt%, 50 to 51 wt%, 51 to 60 wt%, 51 to 59 wt%, 51 to 58 wt%, 51 to 57 wt%, 51 to 56 wt%, 51 to 55 wt%, 51 to 54 wt%, 51 to 53 wt%, 51 to 52 wt%, 52 to 60 wt%, 52 to 59 wt%, 52 to 58 wt%, 52 to 57 wt%, 52 to 56 wt%, 52 to 55 wt%, 52 to 54 wt%, 52 to 53 wt%, 53 to 60 wt%, 53 to 59 wt%, 53 to 58 wt%, 53 to 57 wt%, 53 to 56 wt%, 53 to 55 wt%, 53 to 54 wt%, 54 to 60 wt%, 545 to 60 wt%, 55 to 59 wt%, or a combination thereof, 55 to 58 wt%, 55 to 57 wt%, 55 to 56 wt%, 56 to 60 wt%, 56 to 59 wt%, 56 to 58 wt%, 56 to 57 wt%, 57 to 60 wt%, 57 to 59 wt%, 57 to 58 wt%, 58 to 60 wt%, 58 to 59 wt%, 59 to 60 wt%, or any range or subrange therebetween.

In some embodiments, the solvent composition includes, but is not necessarily limited to: (1) propylene glycol ethers (e.g., propylene glycol monomethyl ether), (2) diethylene glycol dimethyl ether, (3) propylene glycol methyl ether acetate, (4) diethylene glycol diethyl ether, and (5) and any combination thereof (e.g., 2,3, or all 4 of the listed solvents). In some embodiments, the solvent used in the uncured inkjet ink composition is commercially available.

In some embodiments, the uncured inkjet ink composition comprises propylene glycol ethers in the following ranges: 15 to 25 weight percent, 15 to 22 weight percent, 15 to 20 weight percent, 15 to 18 weight percent, 18 to 25 weight percent, 18 to 22 weight percent, 18 to 20 weight percent, 20 to 25 weight percent, 20 to 22 weight percent, 22 to 25 weight percent, or any range or subrange therebetween. In some embodiments, the uncured inkjet ink composition comprises diethylene glycol dimethyl ether in the following ranges: 10 to 20 weight percent, 10 to 18 weight percent, 10 to 16 weight percent, 10 to 12 weight percent, 12 to 20 weight percent, 12 to 18 weight percent, 12 to 16 weight percent, 12 to 14 weight percent, 14 to 20 weight percent, 14 to 18 weight percent, 14 to 16 weight percent, 16 to 20 weight percent, 16 to 18 weight percent, 18 to 20 weight percent, or any range or subrange therebetween. In some embodiments, the uncured inkjet ink composition comprises propylene glycol methyl ether acetate in the following ranges: 13 to 25 weight percent, 13 to 22 weight percent, 13 to 20 weight percent, 13 to 18 weight percent, 13 to 15 weight percent, 15 to 25 weight percent, 15 to 22 weight percent, 15 to 20 weight percent, 15 to 18 weight percent, 18 to 25 weight percent, 18 to 22 weight percent, 18 to 20 weight percent, 20 to 25 weight percent, 20 to 22 weight percent, 22 to 25 weight percent, or any range or subrange therebetween. In some embodiments, the uncured inkjet ink composition comprises diethylene glycol diethyl ether in the range: 0 to 10 weight percent, 0 to 8 weight percent, 0 to 6 weight percent, 0 to 4 weight percent, greater than 0 to 10 weight percent, greater than 0 to 8 weight percent, greater than 0 to 6 weight percent, greater than 0 to 4 weight percent, 2 to 10 weight percent, 2 to 8 weight percent, 2 to 6 weight percent, 2 to 4 weight percent, 4 to 10 weight percent, 4 to 8 weight percent, 4 to 6 weight percent, 6 to 10 weight percent, 6 to 8 weight percent, 8 to 10 weight percent, or any range or subrange therebetween.

In some embodiments, for many other components, the solvent may also include one or more of the following components, including: ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol, 3-methoxy-3-methyl-1-butanol, 1, 2-propanediol, 1, 3-propanediol, 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-dimethylpropane-1, 3-diol, 1, 2-butanediol, 1, 3-butanediol, 2-dimethyl-1, 3-propanediol, 1, 5-pentanediol, 2-methyl-1, 4-pentadiene, 2, 4-diethyl-2, 4-pentanediol, 2-butene-1, 4-diol, 2, 5-hexanediol, 2, 5-dimethylhexane-2, 5-diol, 2-ethyl-1, 3-hexanediol, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol dibutyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol tetrabutyl ether, ethylene glycol monobutyl ether, propylene glycol t-butyl ether, diethylene glycol t-butyl ether, propylene glycol monomethyl ether, propylene glycol methyl butyl ether, dipropylene glycol methyl propylene glycol, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol methyl propylene glycol methyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl, Diethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, and/or ethylene glycol monobutyl ether acetate, and many others.

In some embodiments, the uncured inkjet ink composition may also include a dispersant, intended to keep the pigment component particles uniformly suspended (even after mixing into a paste and/or uncured inkjet ink composition), and to prevent coagulation or precipitation. The coagulated pigment material component particles may clog the inkjet nozzles, causing point defects when printed onto a substrate and drastically reducing the resistivity of the cured inkjet ink composition. The nano-sized pigment material component particles are more susceptible to agglomeration than larger sized pigment material component particles due to, for example, stronger van der waals forces. In some embodiments, the uncured inkjet ink composition comprises a dispersant in the following ranges: 1 to 4 wt%, 1 to 3 wt%, 1 to 2 wt%, 2 to 4 wt%, 2 to 3 wt%, 3 to 4 wt%, or any range or subrange therebetween.

In some embodiments, the dispersant material may include an acrylic polymer material. As just one example, acrylic polymeric material dispersants suitable for compatibility with the uncured resin component and solvent composition are commercially available, depending on the embodiment. According to other embodiments, the dispersant may be or may include one or more of the following, including but not limited to: polyurethane and/or polymethylmethacrylate copolymer dispersants, acrylate copolymers having pigment-philic groups, high molecular weight block copolymers having pigment-philic groups, polycarboxylates of polyamine amides, alkanolammonium salts of copolymers having acidic groups, phosphate ester salts of high molecular weight copolymers having pigment-philic groups, and/or hydroxy-functionalized carboxylic acid esters having pigment-philic groups, and the like. In some embodiments, the dispersant used in the uncured inkjet ink composition is commercially available.

According to some embodiments, the uncured inkjet ink composition may further comprise a flow promoter that improves wetting of the uncured inkjet ink composition on a substrate (e.g., a glass, glass ceramic, metal oxide, metal, and/or polymer substrate) to prevent dewetting of the uncured inkjet ink composition from the substrate prior to curing. In some embodiments, the uncured inkjet ink composition comprises a flow promoter in the following ranges: 0.5 to 3.5 wt%, 0.5 to 3 wt%, 0.5 to 2.5 wt%, 0.5 to 2 wt%, 0.5 to 1.5 wt%, 0.5 to 1 wt%, 1 to 3.5 wt%, 1 to 3 wt%, 1 to 2.5 wt%, 1 to 2 wt%, 1 to 1.5 wt%, 1.5 to 3.5 wt%, 1.5 to 3 wt%, 1.5 to 2.5 wt%, 1.5 to 2 wt%, 2 to 3.5 wt%, 2 to 3 wt%, 2 to 2.5 wt%, 2.5 to 3.5 wt%, 2.5 to 3 wt%, 3 to 3.5 wt%, or any range or subrange therebetween. In some embodiments, the flow promoter may be a modified polyether polydimethylsiloxane. In some embodiments, flow promoters for use in uncured inkjet ink compositions are commercially available.

According to some embodiments, the inkjet ink composition may further comprise surface control agents including, but not limited to: polydimethylsiloxane solutions, polyether polyester modified organosiloxane solutions, alkyl modified organosiloxane solutions, acrylate copolymers, polyacrylate solutions, OH, and/or polyacrylate copolymer solutions having OH functional groups, and the like. The air release agent may be, for example, polydimethylsiloxane and/or modified polydimethylsiloxane.

Further details regarding the uncured inkjet ink composition described and/or otherwise contemplated in accordance with various embodiments are as follows.

Tables 1 and 2 provide various variations of uncured white inkjet ink compositions according to several embodiments.

Table 1: white ink jet ink composition

Table 2: white ink jet ink composition

In addition to the components described above including the pigment component, the resin component, and the solvent composition, the uncured inkjet ink composition may also include one or more other additives, which may or may not be otherwise conventional in uncured inkjet ink compositions, according to some embodiments. Such additional additives may include, but are not necessarily limited to: a resin reinforcement agent, which may comprise up to about 3% and may include conventional compositions.

According to some embodiments herein, the uncured inkjet ink composition may be prepared by: the foregoing components are mixed in any order until a uniform suspension of the uncured inkjet ink composition is obtained. Typically and preferably, the sum of the components is mixed and appropriately adjusted to provide an uncured inkjet ink composition (inkjet printable ink composition) having a viscosity suitable for inkjet printing, for example, 2 to 6 centipoise, 2 to 5 centipoise, 2 to 4 centipoise, 2 to 3 centipoise, 3 to 6 centipoise, 3 to 5 centipoise, 3 to 4 centipoise, 4 to 6 centipoise, 4 to 5 centipoise, or 5 to 6 centipoise at 25 degrees celsius, or any range or subrange therebetween.

In some embodiments, the ink jet ink compositions disclosed herein are thermally curable. Thus, in some embodiments, the ink jet ink compositions disclosed herein are not curable after exposure to ultraviolet light (non-uv curable) and/or are non-aqueous (contain no water). In some embodiments, the thermally curable ink jet ink composition does not contain a photoinitiator component that initiates curing upon exposure to ultraviolet light. In some embodiments, the solvent composition of the ink jet ink composition is non-aqueous.

Ink jet ink composition coating method

The inkjet ink coating method according to embodiments is generally similar to the inkjet ink composition described above. Thus, in some embodiments, an uncured inkjet ink composition according to any of the embodiments described herein is coated onto a substrate. The uncured inkjet ink composition is then cured in situ on the substrate to form a cured inkjet ink composition coating on the substrate. In some embodiments, the ink jet ink composition is applied directly to the substrate surface (e.g., without prior application of a primer). In other embodiments, a primer may be applied to the substrate surface prior to application of the ink jet ink composition to aid in adhesion of the ink to the substrate surface.

According to some embodiments, the coating process may first include the step of formulating an uncured inkjet ink composition. Creating or formulating an uncured inkjet ink composition may include, for example, the steps of: such that the pigment material, inorganic resin component and solvent composition are combined or mixed. The step of producing or formulating an uncured inkjet ink composition may further comprise the preliminary steps of: the dispersant is mixed, milled, or any other means combined with one or more pigments to produce a pigment paste. According to embodiments, pigment pastes premixed with dispersant materials may be commercially available. The pigment paste may be mixed with a mixture of the resin component and the solvent, or the pigment paste may be mixed with a pre-mixed mixture of the resin and the solvent, to form an uncured ink jet ink composition.

In some embodiments, the uncured inkjet ink composition is thermally cured to form a cured inkjet ink composition coating. Such thermal curing of the uncured inkjet ink composition may be performed, for example, in a conventional oven or infrared oven to provide a cured inkjet ink composition coating. In some embodiments, the thermal curing may be performed in an inert atmosphere. In some embodiments, thermal curing of the ink jet ink composition can be a single heating step or multiple heating steps. In some embodiments, the thermal curing may be performed at a temperature range of 160 to 250 degrees celsius for a period of 1 to 20 minutes. In some embodiments, the baking step may be performed after the thermal curing step. In some embodiments, the baking step may be performed at a temperature range of 125 to 175 degrees celsius for a time period of 15 to 60 minutes.

In some embodiments, prior to curing, the ink jet ink composition can be heated at a temperature sufficient to evaporate a portion of the solvent composition but not to thermally cure the ink jet ink composition, thereby minimizing and/or preventing flow once the ink is applied to the substrate. In some embodiments, the substrate can be placed on a hot plate to provide sufficient heat to evaporate a portion of the solvent composition but not to thermally cure the ink jet ink composition. In some embodiments, the hot plate may be heated to a temperature range of 25 to 75 degrees celsius.

Consistent with aspects of the embodiments described above, an uncured inkjet ink composition according to an embodiment is coated on a substrate and cured, the substrate being selected from the group including, but not limited to: glass substrates, glass ceramic substrates, metal oxide substrates, metal substrates, and/or polymer substrates, and the like. The specific end product applications for such substrates vary.

The aforementioned substrate selection options as well as uncured inkjet ink composition coatings and thermal processing curing conditions are not intended to limit the embodiments to any functional end result. Rather, it is an object and intent of embodiments that alternative thermal processing curing conditions may be employed to achieve a particular thermally cured inkjet ink composition coated substrate.

Cured inkjet ink composition coated articles

After going through a series of uncured inkjet ink compositions as described above and a method of coating the inkjet ink compositions as described above to provide a cured inkjet ink composition coated article, is the cured inkjet ink composition coated article itself. Such cured inkjet ink coated articles include a substrate and a cured inkjet ink composition coating on the substrate. The cured coating includes a pigment and a cured inorganic resin binder composition. Desirably, in the coated article according to embodiments, the substrate is selected from the group consisting of: glass substrates, glass ceramic substrates, metal oxide substrates, metal substrates, and/or polymer substrates, and the like. In some embodiments, the coated article may be incorporated into an electronic device, as part of a housing or as a cover component. In some embodiments, the electronic device may include, but is not limited to: a mobile phone, a notebook computer or a tablet.

In some embodiments, the cured coating has an optical density of greater than 0.2 to 1.0, greater than 0.2 to 0.8, greater than 0.2 to 0.6, greater than 0.3 to 1.0, greater than 0.3 to 0.8, greater than 0.3 to 0.6, greater than 0.4 to 1.0, greater than 0.4 to 0.8, greater than 0.4 to 0.6, greater than 0.5 to 1.0, greater than 0.5 to 0.8, greater than 0.5 to 0.6, greater than 0.55 to 1.0, greater than 0.55 to 0.8, greater than 0.6 to 1.0, greater than 0.6 to 0.8, or any range or subrange therebetween. The optical density can be measured using the X-rite 361T transmission scale. In some embodiments, the optical density can be controlled and adjusted by controlling the amount of ink deposited from the inkjet printer printhead. In some embodiments, the thickness of the cured coating is suitable to achieve the desired optical density, for example in the following ranges: 1 to 10 microns, 1 to 8 microns, 1 to 6 microns, 1 to 4 microns, 2 to 10 microns, 2 to 8 microns, 2 to 6 microns, 2 to 4 microns, 3 to 10 microns, 3 to 8 microns, 3 to 6 microns, 3 to 4 microns, 4 to 10 microns, 4 to 8 microns, 4 to 6 microns, or any range or subrange therebetween.

In some embodiments, the cured inkjet ink composition coating has an adhesion to a substrate of 4B or greater as measured using a Gardco cross-hatch adhesion box according to ASTM D3359-09e2 (and subsequent contents thereof), the entire contents of which are incorporated herein by reference. In some embodiments, the cured inkjet ink composition coating meets standard reliability and environmental tests for inks, including a thermal cycling test for 72 hours, a high temperature/high humidity test for 87 hours, a chemical resistance test for 72 hours, a saline test for 72 hours, a snap tape test, and a UV exposure test for 72 hours. According to some embodiments, the pigment component particles are regularly arranged within the cured coating. Finally, the cured inkjet ink resin composition within the cured coated article according to embodiments herein may be chemically characterized using standard methods.

It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the claims.