阅读说明：本技术 一种用于织物涂层喷墨打印的水性粘合剂 (Water-based adhesive for fabric coating ink-jet printing ) 是由 袁宜恩 房迎春 于 2019-10-28 设计创作，主要内容包括：本发明涉及水性粘合技术领域,具体公开了一种用于织物涂层喷墨打印的水性粘合剂,按重量份计,制备原料至少包括：乳化剂6.5-9.5份、软单体180-220份、硬单体210-260份、功能单体15-29份、pH调节剂0.2-0.8份、引发剂1.5-2.5份、残余单体处理剂0.5-1.4份、水400-500份；本发明通过控制乳化剂的种类和比例以及对软单体、硬单体、功能单体的特定选择,使得水性粘合剂在织物涂层喷墨打印技术中具有颜色鲜艳、耐水洗的功效。(The invention relates to the technical field of water-based adhesives, and particularly discloses a water-based adhesive for fabric coating ink-jet printing, which at least comprises the following preparation raw materials in parts by weight: 6.5-9.5 parts of emulsifier, 220 parts of soft monomer, 260 parts of hard monomer, 15-29 parts of functional monomer, 0.2-0.8 part of pH regulator, 1.5-2.5 parts of initiator, 0.5-1.4 parts of residual monomer treating agent and 500 parts of water 400; the invention controls the kind and proportion of the emulsifier and the specific selection of the soft monomer, the hard monomer and the functional monomer, so that the water-based adhesive has the effects of bright color and water washing resistance in the textile coating ink-jet printing technology.)

1. An aqueous binder for inkjet printing of textile coatings, characterized in that the preparation of the binder comprises at least, in parts by weight: 6.5 to 9.5 portions of emulsifier, 220 portions of soft monomer, 260 portions of hard monomer, 15 to 29 portions of functional monomer, 0.2 to 0.8 portion of pH regulator, 1.5 to 2.5 portions of initiator, 0.5 to 1.4 portions of residual monomer treating agent and 500 portions of water 400.

2. The aqueous binder for inkjet printing of fabric coatings according to claim 1 characterized in that the emulsifier is an anionic emulsifier and/or a non-ionic emulsifier.

3. The aqueous binder for inkjet printing of fabric coatings according to claim 1 characterized in that the non-ionic emulsifier is a fatty alcohol polyoxyethylene ether compound.

4. The aqueous binder for inkjet printing of fabric coatings according to claim 1 wherein the soft monomer is selected from one or more of ethyl acrylate, butyl acrylate, octyl acrylate, isooctyl acrylate, butyl methacrylate.

5. The aqueous binder for inkjet printing of fabric coatings according to claim 1 wherein the hard monomer is selected from one or more of methyl methacrylate, vinyl acetate, styrene, acrylonitrile, vinyl acetate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexafluorobutyl methacrylate.

6. The aqueous binder for inkjet printing of fabric coatings according to claim 1 characterized in that the functional monomer is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, N-methylol acrylamide, glycidyl methacrylate, diallyl phthalate.

7. The aqueous binder for inkjet printing of fabric coatings according to claim 1 characterized in that the pH adjusting agent is selected from one or more of calcium carbonate, sulfur dioxide, sodium hydroxide, disodium hydrogen phosphate, sodium bicarbonate.

8. The aqueous binder for inkjet printing of fabric coatings according to claim 1 characterized in that the initiator is selected from one or more of persulfates, azo compounds, benzoyl peroxide.

9. The aqueous binder for inkjet printing of fabric coatings according to claim 1 characterized in that the residual monomer treatment agent is selected from one or more of alkyl peroxides, vitamins.

10. A method of preparing an aqueous binder for inkjet printing of fabric coatings according to any of claims 1 to 8, characterized in that it comprises the following steps:

(1) mixing a soft monomer, a hard monomer, a functional monomer, an emulsifier and water to obtain a mixed solution 1;

(2) mixing an initiator and water to obtain a mixed solution 2;

(3) mixing the residual monomer treating agent with water to obtain a mixed solution 3;

(4) adding water, an emulsifier and a pH regulator into a reaction container, introducing nitrogen, heating to 70-90 ℃, adding 1-5% of a mixed solution 1 and 1-5% of a mixed solution 2, reacting for 10-30min, adding the rest of the mixed solution 1 and the rest of the mixed solution 2, reacting for 200-300min at 80-90 ℃, adding a mixed solution 3 when cooling to 60-75 ℃, preserving heat for 20-35min, cooling to 20-45 ℃, and filtering to obtain the catalyst.

Technical Field

The invention relates to the technical field of aqueous adhesives, in particular to an aqueous adhesive for fabric coating ink-jet printing.

Background

As society advances, printed substrates extend from paper to woven fabrics. For printing and dyeing of textile fabrics, a plurality of modes such as pigment printing, transfer printing and the like are used, and the defects are that the modes are inflexible, large-scale single production is required, and the pollution is heavy. In order to meet the requirements of simplicity, convenience and flexibility, an ink-jet printing technology on a cloth cover is created, ink is ejected from an ink-jet printer in the form of tiny ink drops (nanometer micron size), contacts with the surface of a printing medium material, diffuses, adsorbs and dries in different directions, and finally forms a required image, the imaging quality is closely related to an ink-absorbing coating on the surface of the printing medium material, and the ink-absorbing coating determines the color brightness, the water resistance and the resolution of the printed image, the application field of the printing medium material and the like.

However, although the prior art uses a water-resistant adhesive, which is easy to make the coating and the printed image have a certain water-resistant effect, the adhesive has many defects in the aspects of color expression of the image and weather resistance, light resistance and aging resistance of the coating, such as easy whitening, non-bright color, yellowing, brittleness, poor durability and the like of the coating; therefore, the development of an adhesive which has water resistance and can make the printing color bright, durable and high in resolution is the focus of attention of the production industry.

Disclosure of Invention

In order to solve the technical problem, the first aspect of the present invention provides an aqueous binder for inkjet printing of fabric coatings, which is prepared from at least the following raw materials in parts by weight: 6.5 to 9.5 portions of emulsifier, 220 portions of soft monomer, 260 portions of hard monomer, 15 to 29 portions of functional monomer, 0.2 to 0.8 portion of pH regulator, 1.5 to 2.5 portions of initiator, 0.5 to 1.4 portions of residual monomer treating agent and 500 portions of water 400.

As a preferred technical scheme of the invention, the emulsifier is an anionic emulsifier and/or a nonionic emulsifier.

As a preferable technical scheme, the nonionic emulsifier is a fatty alcohol polyoxyethylene ether compound.

In a preferred embodiment of the present invention, the soft monomer is selected from one or more of ethyl acrylate, butyl acrylate, octyl acrylate, isooctyl acrylate, and butyl methacrylate.

In a preferred embodiment of the present invention, the hard monomer is one or more selected from the group consisting of methyl methacrylate, vinyl acetate, styrene, acrylonitrile, vinyl acetate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, and hexafluorobutyl methacrylate.

In a preferred embodiment of the present invention, the functional monomer is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, N-methylolacrylamide, glycidyl methacrylate, and diallyl phthalate.

In a preferred embodiment of the present invention, the pH adjuster is one or more selected from calcium carbonate, sulfur dioxide, sodium hydroxide, disodium hydrogen phosphate, and sodium bicarbonate.

In a preferred embodiment of the present invention, the initiator is selected from one or more of persulfates, azo compounds, and benzoyl peroxide.

As a preferred technical scheme of the invention, the residual monomer treatment agent is selected from one or more of alkyl peroxide and vitamin.

In a second aspect, the present invention provides a method for preparing an aqueous binder for inkjet printing of a fabric coating, characterized in that the preparation method comprises the following steps:

(1) mixing a soft monomer, a hard monomer, a functional monomer, an emulsifier and water to obtain a mixed solution 1;

(2) mixing an initiator and water to obtain a mixed solution 2;

(3) mixing the residual monomer treating agent with water to obtain a mixed solution 3;

(4) adding water, an emulsifier and a pH regulator into a reaction container, introducing nitrogen, heating to 70-90 ℃, adding 1-5% of a mixed solution 1 and 1-5% of a mixed solution 2, reacting for 10-30min, adding the rest of the mixed solution 1 and the rest of the mixed solution 2, reacting for 200-300min at 80-90 ℃, adding a mixed solution 3 when cooling to 60-75 ℃, preserving heat for 20-35min, cooling to 20-45 ℃, and filtering to obtain the catalyst.

Has the advantages that: the invention provides a water-based adhesive for fabric coating ink-jet printing, which has good crosslinking performance by controlling the type and proportion of an emulsifier and specific selection of a soft monomer, a hard monomer and a functional monomer, has firm adhesion after film formation on the surface of a fabric, can ensure that printing has higher color fastness and bright color when applied to the fabric coating ink-jet printing technology, and also has the advantages of water washing resistance, strong weather resistance, difficult shedding of the printing, higher printing quality and the like.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

In order to solve the technical problem, the first aspect of the present invention provides an aqueous binder for inkjet printing of fabric coatings, which is prepared from at least the following raw materials in parts by weight: 6.5 to 9.5 portions of emulsifier, 220 portions of soft monomer, 260 portions of hard monomer, 15 to 29 portions of functional monomer, 0.2 to 0.8 portion of pH regulator, 1.5 to 2.5 portions of initiator, 0.5 to 1.4 portions of residual monomer treating agent and 500 portions of water 400.

In a preferred embodiment, the aqueous binder for inkjet printing of fabric coating is prepared by at least the following raw materials in parts by weight: 7-9.3 parts of emulsifier, 190 parts of soft monomer, 210 parts of hard monomer, 215 parts of hard monomer, 20-28 parts of functional monomer, 0.3-0.6 part of pH regulator, 1.7-1.9 parts of initiator, 0.7-1.2 parts of residual monomer treating agent and 460 parts of water.

In a most preferred embodiment, the aqueous binder for inkjet printing of fabric coatings is prepared from at least the following raw materials in parts by weight: 9 parts of emulsifier, 200 parts of soft monomer, 220 parts of hard monomer, 25 parts of functional monomer, 0.5 part of pH regulator, 2 parts of initiator, 1 part of residual monomer treating agent and 450 parts of water.

Emulsifier

The emulsifier of the present invention is a material capable of improving the surface tension between the various constituent phases in an emulsion to form a uniform and stable dispersion or emulsion. The emulsifier is a surface active substance, has both hydrophilic groups and lipophilic groups in the molecule, is gathered on an oil/water interface, can reduce interfacial tension and reduce the energy required for forming an emulsion, thereby improving the energy of the emulsion, but different types of emulsifiers have obviously different phenomena in the practical application process, so the invention further explores the selection of the types of the emulsifiers.

In a preferred embodiment, the emulsifier of the present invention is a combination of an anionic emulsifier and a nonionic emulsifier.

In a preferred embodiment, the nonionic emulsifier of the present invention is a fatty alcohol polyoxyethylene ether compound.

As examples of the fatty alcohol-polyoxyethylene ether, fatty alcohol-polyoxyethylene ether 5EO, fatty alcohol-polyoxyethylene ether 7EO, fatty alcohol-polyoxyethylene ether 9EO, fatty alcohol-polyoxyethylene ether 10EO, fatty alcohol-polyoxyethylene ether 15EO, fatty alcohol-polyoxyethylene ether 20EO, fatty alcohol-polyoxyethylene ether 30EO, fatty alcohol-polyoxyethylene ether 40EO can be cited.

In a preferred embodiment, the anionic emulsifier of the present invention is selected from one or more of alkyl benzene sulfonate, alkyl sulfonate ester salt, alkyl sulfonate, alkyl sulfate, fluorine-containing fatty acid salt, polysiloxane, fatty alcohol sulfate, α -alkenyl sulfonate, alkyl alcohol amide, alkyl sulfonic acetamide, alkyl succinate sulfonate, alcohol amine alkyl benzene sulfonate, naphthenate, alkyl phenol sulfonate, polyoxyethylene monolaurate.

As examples of the alkylbenzenesulfonate, there can be mentioned 4-dodecylbenzenesulfonic acid sodium salt (CAS number: 2211-98-5), hexadecylsulfophenoxybenzenesulfonic acid disodium salt (CAS number: 65143-89-7), dodecylbenzenesulfonic acid ammonium salt (CAS number: 1331-61-9).

As examples of alkyl sulfates, mention may be made of: ammonium lauryl sulfate, sodium lauryl sulfate (CAS number: 151-21-3), sodium octadecyl sulfate (CAS number: 1120-04-3), and lithium lauryl sulfate (CAS number: 2044-56-6).

As examples of the alkylsulfonic acid salts, there may be enumerated: sodium 1-decanesulfonate (CAS number: 13419-61-9), n-octadecyl sulfonic acid sodium salt (CAS number: 13893-34-0), sodium dodecyl sulfonate (CAS number: 2386-53-0).

In a more preferred embodiment, the emulsifier of the present invention is a composition of ammonium lauryl sulfate and fatty alcohol-polyoxyethylene ether 30EO, wherein the mass ratio of ammonium lauryl sulfate to fatty alcohol-polyoxyethylene ether 30EO is 1: (1-4).

In a more preferred embodiment, the emulsifier of the present invention is a composition of ammonium lauryl sulfate and fatty alcohol-polyoxyethylene ether 30EO, wherein the mass ratio of ammonium lauryl sulfate to fatty alcohol-polyoxyethylene ether 30EO is 1: (1.5-3).

In a most preferred embodiment, the emulsifier of the present invention is a composition of ammonium lauryl sulfate and fatty alcohol-polyoxyethylene ether 30EO, wherein the mass ratio of ammonium lauryl sulfate to fatty alcohol-polyoxyethylene ether 30EO is 1: 2.

the invention makes relevant research on the selection of the emulsifier, and experiments prove that aiming at the monomer combination selected by the invention, the combination of the anionic emulsifier and the nonionic emulsifier is selected, so that the fabric with excellent cohesiveness and bright printing color can be obtained. The possible reason is that the anionic emulsifier is matched with the nonionic emulsifier, so that electrostatic repulsion is generated between emulsion particles, and a proper hydration layer is realized on the surfaces of the emulsion particles, thereby being beneficial to improving the stability of the emulsion and promoting the polymerization degree of the monomer; the monomer in the pre-emulsification stage exists stably, the emulsion is not layered and has no foam, and the conversion rate of the emulsion in the polymerization stage is improved; however, when the amount of the anionic emulsifier is small, the monomer is insufficiently emulsified, the polymerization degree is low, the emulsion stability is poor, when the amount of the anionic emulsifier is large, the polymerization speed is high, the reaction is difficult to control, and the adhesive property of the adhesive after film forming is poor; it is unexpectedly found through experiments that when the mass ratio of the anionic emulsifier to the nonionic emulsifier is 1: (1-4), the effect is excellent.

Soft monomer

The soft monomer refers to a monomer with lower homopolymer glass transition temperature.

In a preferred embodiment, the soft monomer of the present invention is selected from one or more of ethyl acrylate, butyl acrylate, octyl acrylate, isooctyl acrylate, butyl methacrylate.

In a most preferred embodiment, the soft monomer of the present invention is butyl acrylate.

Hard monomer

The hard monomer refers to a monomer with a higher homopolymer glass transition temperature.

In a preferred embodiment, the hard monomer of the present invention is selected from one or more of methyl methacrylate, vinyl acetate, styrene, acrylonitrile, vinyl acetate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, and hexafluorobutyl methacrylate.

In a most preferred embodiment, the hard monomer of the present invention is styrene (CAS number: 100-42-5).

Functional monomer

The functional monomer is a monomer capable of providing a functional group.

In a preferred embodiment, the functional monomers of the present invention are one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, N-methylolacrylamide, glycidyl methacrylate, diallyl phthalate.

In a more preferred embodiment, the functional monomers of the present invention are acrylic acid and methylolacrylamide, wherein the mass ratio of acrylic acid to methylolacrylamide is 1: (0.5-3).

In a more preferred embodiment, the functional monomers of the present invention are acrylic acid and methylolacrylamide, wherein the mass ratio of acrylic acid to methylolacrylamide is 1: (1-2.5).

In a most preferred embodiment, the functional monomers of the present invention are acrylic acid and methylolacrylamide, wherein the mass ratio of acrylic acid to methylolacrylamide is 1: 1.5.

the inventor of the application finds in experiments that a stable three-dimensional network structure is easily formed on the surface of a fiber by selecting specific soft monomers, hard monomers and functional monomers containing carboxyl and amino, the affinity of the adhesive and the fiber is greatly improved, the adhesive with excellent film forming property and adhesion can be obtained, the coating of the adhesive on dye in a printing adhesive film can be enhanced by controlling the types and the proportion of the monomers, and the water resistance and the vividness of a printed fabric are improved.

pH regulator

The pH regulator is also called acidity regulator and is used for maintaining or changing the pH value of the product.

In a preferred embodiment, the pH adjusting agent of the present invention is selected from one or more of calcium carbonate, sulfur dioxide, sodium hydroxide, disodium hydrogen phosphate, and sodium hydrogen carbonate.

In a most preferred embodiment, the pH adjusting agent of the present invention is sodium bicarbonate.

Initiator

The initiator is also called initiator, is also called free radical initiator, and refers to a compound which is easy to be decomposed into free radicals (namely primary free radicals) by heating, can be used for initiating free radical polymerization and copolymerization of alkene and diene monomers, and can also be used for crosslinking curing and macromolecule crosslinking reaction of unsaturated polyester.

In a preferred embodiment, the initiator according to the present invention is selected from one or more of persulfates, azo compounds, and benzoyl peroxide.

As examples of the persulfate, there can be cited: potassium persulfate, sodium persulfate and ammonium persulfate.

As examples of azo compounds, there may be mentioned: azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyronitrile formamide, and dimethyl azobisisobutyrate.

In a most preferred embodiment, the initiator of the present invention is ammonium persulfate.

Residual monomer treating agent

The residual monomer treatment agent in the present invention means a substance which can treat the residual monomer in the system.

In a preferred embodiment, the residual monomer treatment agent of the present invention is selected from one or more of organic peroxides, vitamins.

As examples of the alkyl peroxide, di-t-amyl peroxide (CAS: 10508-09-5), di-t-butyl peroxide (CAS: 110-05-4), and t-butyl hydroperoxide (CAS: 75-91-2) can be cited.

In a most preferred embodiment, the alkyl peroxide of the present invention is t-butyl hydroperoxide (CAS: 75-91-2).

As examples of vitamins, there may be mentioned: vitamin A, vitamin B, vitamin C, vitamin D and vitamin E.

In a preferred embodiment, the vitamin of the invention is vitamin C (CAS number: 50-81-7).

In a more preferred embodiment, the residual monomer treatment agent of the present invention is t-butyl hydroperoxide and vitamin C, wherein the mass ratio of t-butyl hydroperoxide to vitamin C is (1-5): 1.

in a more preferred embodiment, the residual monomer treatment agent of the present invention is t-butyl hydroperoxide and vitamin C, wherein the mass ratio of t-butyl hydroperoxide to vitamin C is (2-3.5): 1.

in a most preferred embodiment, the residual monomer treatment agent of the present invention is t-butyl hydroperoxide and vitamin C, wherein the mass ratio of t-butyl hydroperoxide to vitamin C is 2.3: 1.

in a second aspect of the invention, there is provided a process for the preparation of an aqueous binder for inkjet printing of a fabric coating, the process comprising the steps of:

(1) mixing a soft monomer, a hard monomer, a functional monomer, an emulsifier and water to obtain a mixed solution 1;

(2) mixing an initiator and water to obtain a mixed solution 2;

(3) mixing the residual monomer treating agent with water to obtain a mixed solution 3;

(4) adding water, an emulsifier and a pH regulator into a reaction container, introducing nitrogen, heating to 70-90 ℃, adding 1-5% of a mixed solution 1 and 1-5% of a mixed solution 2, reacting for 10-30min, adding the rest of the mixed solution 1 and the rest of the mixed solution 2, reacting for 200-300min at 80-90 ℃, adding a mixed solution 3 when cooling to 60-75 ℃, preserving heat for 20-35min, cooling to 20-45 ℃, and filtering to obtain the catalyst.

It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.