CN109295766B - Waterborne polyurethane acrylate printing adhesive - Google Patents
Waterborne polyurethane acrylate printing adhesive Download PDFInfo
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- CN109295766B CN109295766B CN201811174534.0A CN201811174534A CN109295766B CN 109295766 B CN109295766 B CN 109295766B CN 201811174534 A CN201811174534 A CN 201811174534A CN 109295766 B CN109295766 B CN 109295766B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
- D06P1/67383—Inorganic compounds containing silicon
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
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Abstract
The invention relates to a pigment printing adhesive, in particular to a waterborne polyurethane acrylate printing adhesive, which comprises a solvent and polymer particles, wherein the solvent comprises deionized water, the polymer particles are of a three-layer structure of a core layer, a middle layer and a hydrophobic layer, the core layer is waterborne polyurethane, the middle layer is a fluorine-containing acrylate layer, the hydrophobic layer is a silicon dioxide particle layer, the waterborne polyurethane and the fluorine-containing acrylate in the middle layer are mutually combined through sulfonic group and hydroxyl crosslinking, and the fluorine-containing acrylate in the middle layer and the silicon dioxide particles in the hydrophobic layer are mutually combined through epoxy ring-opening reaction.
Description
Technical Field
The invention relates to a pigment printing adhesive, in particular to a waterborne polyurethane acrylate printing adhesive.
Background
The acrylate adhesive has received great attention due to its many advantages, such as high adhesion, fast curing speed, wide adaptability, excellent mechanical properties and no selectivity to the adhesion object, but many defects are also revealed, such as sticky adhesive film, poor water resistance and temperature resistance, poor moisture permeability and air permeability, poor low temperature film forming property, poor anti-tack property at high temperature, and relatively low elongation. In view of these problems, many modifications have been made to the structure of such adhesives, but most modifications are only directed to one of the defects, and few studies have been made to improve the properties such as water resistance, temperature resistance, and elongation at break. The waterborne polyurethane adhesive has the advantages of good water resistance and adhesion, stable emulsion without precipitation, good mechanical property of an adhesive film, no adhesion to hands and the like, and effectively overcomes the defects of the acrylate adhesive, but the cost of the waterborne polyurethane adhesive is higher, so the production cost of the adhesive can be effectively reduced by adopting the acrylate modified waterborne polyurethane, the performances of the two adhesives can be combined simultaneously, the hydrophobic anti-fouling capability is also an important index after the film is formed by the adhesive, in the prior art, the surface energy of the adhesive is reduced only by introducing fluorine-containing groups into the adhesive, but the improved hydrophobicity of the method is limited because the film formed by the adhesive is thick and smooth.
The invention discloses a preparation method of acrylate modified waterborne polyurethane at 12/5/2012 by the Chinese patent office, wherein the publication number of the invention is CN 102807664A. The material is acrylate modified waterborne polyurethane with a main chain introduced with active double bonds, butylene glycol is used as a chain extender, the active double bonds are introduced on the main chain of polyurethane molecules, the active double bonds are introduced on the polyurethane chain, and then acrylate monomers are used for connecting the main chains of the polyurethane together through double bond polymerization to form a net structure, so that an acrylate modified waterborne polyurethane product is synthesized. The synthetic method of the invention is simple and convenient to realize, the product performance is good, the cost is low, no pollution is generated in the production and use processes, and the synthetic material has wide application prospects in the industries of coatings, adhesives and synthetic leather, but the surface of the material of the patent has no hydrophobicity, and the characteristics of water resistance, dirt resistance, corrosion resistance and the like for a long time cannot be provided.
Disclosure of Invention
In order to solve the problems of poor hydrophobic property, poor tack-back property, stiff hand feeling and the like of the acrylic ester polymer in the prior art, the waterborne polyurethane acrylic ester printing adhesive with the three-layer structure and super-hydrophobicity is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
the aqueous polyurethane acrylate printing adhesive comprises a solvent and polymer particles, wherein the solvent comprises deionized water, the polymer particles are of a three-layer structure including a core layer, a middle layer and a hydrophobic layer, aqueous polyurethane is arranged in the core layer, the middle layer is a fluorine-containing acrylate layer, the hydrophobic layer is a silicon dioxide particle layer, the aqueous polyurethane in the core layer and fluorine-containing acrylate in the middle layer are combined with each other through sulfonic acid groups and hydroxyl groups in a cross-linking mode, and the fluorine-containing acrylate in the middle layer and the silicon dioxide particles in the hydrophobic layer are combined with each other through an epoxy ring-opening reaction.
The waterborne polyurethane acrylate printing adhesive disclosed by the invention comprises solvent water and polymer particles, wherein the polymer particles comprise three-layer structures of a core layer, a middle layer and a hydrophobic layer, the core layer is a waterborne polyurethane layer, the waterborne polyurethane has the characteristics of good flexibility, low temperature resistance, strong adhesion and the like, the middle layer is an acrylic resin layer, the middle layer comprises a sulfonic acid group and an epoxy group, and the sulfonic acid group can be subjected to a crosslinking reaction with hydroxyl in the waterborne polyurethane of the core layer after a proper crosslinking agent is added, so that the coating force of the middle layer and the core layer is greatly increased, the migration of the hydrophilic group to the surface can be inhibited, and the surface hydrophobicity of the material is greatly increased by matching with the low surface energy of the fluorine-containing group; the hydrophobic layer is a silicon dioxide particle coating layer, the silicon dioxide particles react with the epoxy groups contained in the middle layer to form chemical bonds to coat the surfaces of the polymer particles to form rough structure surfaces, and the hydrophobicity of the material is greatly increased.
Preferably, the core layer preparation comprises the following components in parts by mass: 50-70 parts of water, 15-25 parts of a first monomer composition, 0.5-1.5 parts of 1, 4-butanediol, 0.1-0.5 part of dimethylolpropionic acid, 0.3-0.8 part of dibutyltin dilaurate, 1-3 parts of a salt forming agent and 1-5 parts of a terminated monomer; the intermediate layer comprises the following components in parts by mass: 50-60 parts of N, N-dimethyl acetamide, 20-35 parts of a second monomer composition, 0.1-0.3 part of azobisisobutyronitrile, 3-10 parts of glycidyl methacrylate and 0.5-1 part of a crosslinking agent; the hydrophobic layer comprises the following components in parts by mass: 90-98 parts of 90-97wt% ethanol aqueous solution, 4-8 parts of gamma-aminopropyltriethoxysilane, 2-4 parts of silicon dioxide particles and 1-3 parts of diethylamine.
The glycidyl methacrylate containing epoxy groups is introduced, which is beneficial to coating modified silicon dioxide.
Preferably, the first monomer composition in the core layer comprises the following components in mass ratio: 40-60 parts of polytetrahydrofuran ether glycol, 30-40 parts of isophorone diisocyanate and 10-20 parts of polydimethylsiloxane.
Preferably, the salt forming agent in the core layer is triethylamine, diethylamine or ammonia water.
The salt forming agent reacts with isocyanate to neutralize the reaction system, so that the polyurethane emulsion exists more stably.
Preferably, the end capping monomer in the core layer is hydroxyethyl methacrylate.
The hydroxyethyl methacrylate is used for reacting with isocyanic acid radical in the waterborne polyurethane and introducing double bonds.
Preferably, the second monomer composition in the intermediate layer comprises the following components in mass ratio: 30-40 parts of perfluorohexyl ethyl acrylate, 35-45 parts of methyl methacrylate and 20-30 parts of 2-acrylamide-2-methylpropanesulfonic acid.
The middle layer monomer uses 2-acrylamide-2-methylpropanesulfonic acid with sulfonic acid groups, the sulfonic acid groups can be crosslinked with hydroxyl in the waterborne polyurethane, the binding force is increased, the hydrophilic groups can be prevented from migrating to the surface, and the middle layer monomer also uses fluorine-containing monomer perfluorohexyl ethyl acrylate, so that the surface energy is reduced, and the hydrophobicity is further increased.
Preferably, the cross-linking agent in the intermediate layer is methylated hexamethylol melamine.
The methylated hexamethylol melamine can promote the crosslinking of sulfonic acid groups and hydroxyl groups.
Preferably, the silica particles in the hydrophobic layer are mesoporous silica particles.
Preferably, the silica particles in the hydrophobic layer are nano silica particles.
The invention has the beneficial effects that: (1) the polymer particles in the printing adhesive have a three-layer structure, and the core layer is waterborne polyurethane, so that the printing adhesive is good in flexibility; (2) the middle layer is a fluorine-containing acrylate layer with sulfonic acid groups and epoxy groups, the sulfonic acid groups can be crosslinked with hydroxyl groups in the core layer waterborne polyurethane to increase the coating strength, and the epoxy groups can be combined with the outer aminated silica particles through reaction; (3) the outermost layer of the polymer particles is coated with the silica particles, so that the surface roughness of the adhesive is increased, and the surface energy of the fluorine-containing groups in the middle layer is low, so that good hydrophobic property is provided for the material.
Detailed Description
The present invention will be described more clearly and completely with reference to the following specific embodiments, which are obviously only a part of the embodiments of the present invention, but not all of them. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
Example 1: the preparation method of the aqueous polyurethane acrylate printing adhesive comprises the following steps:
(1) placing polytetrahydrofuran ether glycol into a drying oven, dehydrating at 70 ℃ and removing oxygen for 1 h;
(2) adding 50g of a first monomer composition into 200g of deionized water, wherein the first monomer composition comprises 40 parts of polytetrahydrofuran ether glycol, 50 parts of isophorone diisocyanate and 10 parts of polydimethylsiloxane by mass, then adding 3.2g of 1, 4-butanediol, 0.8g of bis (hydroxymethyl) propionic acid, 1.5g of dibutyltin dilaurate and argon protection, and reacting for 1.2h at 60 ℃ to obtain a polyurethane prepolymer;
(3) adding 3.2g of hydroxyethyl methacrylate into the polyurethane prepolymer, and reacting at 60 ℃ for 0.5h to obtain double-bond end-capped polyurethane;
(4) adding 15g of diethylamine aqueous solution with neutralization degree of 90% to obtain waterborne polyurethane;
(5) adding 65g of a second monomer composition into 150g of N, N-dimethylacetamide, wherein the second monomer composition comprises the following components in parts by mass: 30 parts of perfluorohexyl ethyl acrylate, 45 parts of methyl methacrylate and 25 parts of 2-acrylamide-2-methylpropanesulfonic acid, fully mixing, adding 0.52g of azobisisobutyronitrile under the protection of argon, reacting for 8 hours at 60 ℃, pouring into a dialysis bag for dialysis for 5 days, and freeze-drying for 20 hours at-50 ℃ to obtain an emulsifier;
(6) adding 50g of emulsifier and 10g of glycidyl methacrylate into the waterborne polyurethane obtained in the step (4), and adding 0.13g of azobisisobutyronitrile and 1.3g of methylated hexamethylolmelamine to obtain waterborne polyurethane acrylate emulsion;
(7) 2g of silicon dioxide particles are dissolved in 20g of 95 wt% ethanol water solution, and ultrasonic dispersion is carried out for 30 min;
(8) adding diethylamine dropwise to adjust the pH to 8.5;
(9) dropwise adding 5g of gamma-aminopropyltriethoxysilane into the silicon dioxide ethanol solution, and reacting for 5 hours at 75 ℃;
(10) carrying out suction filtration to obtain modified silicon dioxide particles, washing the modified silicon dioxide particles by using 95 wt% ethanol aqueous solution, and drying at 100 ℃ to obtain aminated silicon dioxide particles;
(11) and (3) adding 2g of gamma-aminopropyltriethoxysilane-modified silicon dioxide particles into the emulsion obtained in the step (6), adding 5g of diethylamine, and magnetically stirring at room temperature until the diethylamine is completely dissolved to prepare the aqueous polyurethane acrylate printing adhesive.
Example 2: the preparation method of the aqueous polyurethane acrylate printing adhesive comprises the following steps:
(1) placing polytetrahydrofuran ether glycol into a drying oven, dehydrating at 80 ℃ and removing oxygen for 2 h;
(2) adding 70g of a first monomer composition into 300g of deionized water, wherein the first monomer composition comprises 50 parts of polytetrahydrofuran ether glycol, 30 parts of isophorone diisocyanate and 20 parts of polydimethylsiloxane in a mass ratio, then adding 4g of 1, 4-butanediol, 1.3g of bis (hydroxymethyl) propionic acid, 2.1g of dibutyltin dilaurate and argon protection, and reacting for 2 hours at 70 ℃ to obtain a polyurethane prepolymer;
(3) adding 4.1g of hydroxyethyl methacrylate into the polyurethane prepolymer, and reacting at 70 ℃ for 1h to obtain double-bond end-capped polyurethane; (4) adding 40g of diethylamine aqueous solution with the neutralization degree of 95% to obtain waterborne polyurethane;
(5) adding 95g of a second monomer composition into 180g of N, N-dimethylacetamide, wherein the second monomer composition comprises the following components in parts by mass: fully mixing 40 parts of perfluorohexyl ethyl acrylate, 40 parts of methyl methacrylate and 20 parts of 2-acrylamide-2-methylpropanesulfonic acid, adding 0.76g of azobisisobutyronitrile under the protection of argon, reacting at 70 ℃ for 10 hours, pouring into a dialysis bag for dialysis for 8 days, and freeze-drying at-45 ℃ for 25 hours to obtain an emulsifier;
(6) adding 80g of emulsifier and 20g of glycidyl methacrylate into the waterborne polyurethane obtained in the step (4), and adding 0.18g of azobisisobutyronitrile and 2.2g of methylated hexamethylolmelamine to obtain waterborne polyurethane acrylate emulsion;
(7) dissolving 3g of silicon dioxide particles in 40g of 97wt% ethanol aqueous solution, and performing ultrasonic dispersion for 50 min;
(8) adding diethylamine dropwise to adjust the pH to 8.9;
(9) dropwise adding 7g of gamma-aminopropyltriethoxysilane into the silicon dioxide ethanol solution, and reacting for 5 hours at 70 ℃;
(10) carrying out suction filtration to obtain modified silicon dioxide particles, washing the modified silicon dioxide particles by using 95 wt% ethanol aqueous solution, and drying at 110 ℃ to obtain aminated silicon dioxide particles;
(11) and (3) adding 3g of gamma-aminopropyltriethoxysilane-modified silicon dioxide particles into the emulsion obtained in the step (6), adding 5.5g of diethylamine, and magnetically stirring at room temperature until the diethylamine is completely dissolved to prepare the aqueous polyurethane acrylate printing adhesive.
Example 3: the preparation method of the aqueous polyurethane acrylate printing adhesive comprises the following steps:
(1) placing polytetrahydrofuran ether glycol into a drying oven, dehydrating at 75 ℃ and removing oxygen for 1.5 h;
(2) adding 85g of a first monomer composition into 350g of deionized water, wherein the first monomer composition comprises 60 parts of polytetrahydrofuran ether glycol, 30 parts of isophorone diisocyanate and 10 parts of polydimethylsiloxane in a mass ratio, then adding 4.6g of 1, 4-butanediol, 3.1g of bis (hydroxymethyl) propionic acid, 2.3g of dibutyltin dilaurate and argon protection, and reacting for 3 hours at 80 ℃ to obtain a polyurethane prepolymer;
(3) adding 2.1g of hydroxyethyl methacrylate into the polyurethane prepolymer, and reacting at 80 ℃ for 1.5h to obtain double-bond end-capped polyurethane;
(4) adding 30g of diethylamine aqueous solution with the neutralization degree of 98 percent to obtain waterborne polyurethane;
(5) adding 120g of a second monomer composition into 200g of N, N-dimethylacetamide, wherein the second monomer composition comprises the following components in parts by mass: fully mixing 25 parts of perfluorohexyl ethyl acrylate, 45 parts of methyl methacrylate and 30 parts of 2-acrylamide-2-methylpropanesulfonic acid, adding 0.96g of azobisisobutyronitrile under the protection of argon, reacting at 78 ℃ for 12 hours, pouring into a dialysis bag for dialysis for 9 days, and freeze-drying at-50 ℃ for 28 hours to obtain an emulsifier;
(6) adding 110g of emulsifier and 30g of glycidyl methacrylate into the waterborne polyurethane obtained in the step (4), and adding 0.21g of azobisisobutyronitrile and 4g of methylated hexamethylolmelamine to obtain waterborne polyurethane acrylate emulsion;
(7) 2.5g of silicon dioxide particles are dissolved in 30g of 95 wt% ethanol water solution, and ultrasonic dispersion is carried out for 50 min;
(8) adding diethylamine dropwise to adjust the pH to 9;
(9) dropwise adding 6g of gamma-aminopropyltriethoxysilane into the silicon dioxide ethanol solution, and reacting for 4 hours at 80 ℃;
(10) carrying out suction filtration to obtain modified silicon dioxide particles, washing the modified silicon dioxide particles by using 97wt% ethanol aqueous solution, and drying at 120 ℃ to obtain aminated silicon dioxide particles;
(11) and (3) adding 2.5g of gamma-aminopropyltriethoxysilane modified silicon dioxide particles into the emulsion obtained in the step (6), adding 5g of diethylamine, and magnetically stirring at room temperature until the mixture is completely dissolved to prepare the aqueous polyurethane acrylate printing adhesive.
Comparative example 1: the difference from the example 1 is that the second monomer ratio in the step (5) is 40 parts of perfluorohexyl ethyl acrylate and 60 parts of methyl methacrylate, 2-acrylamide-2-methyl propane sulfonic acid is not contained, and methyl etherified hexamethylol melamine is not added in the step (6).
Comparative example 2: the difference from example 1 is that glycidyl methacrylate in step (6) is replaced by methacrylate which does not contain epoxy groups.
Comparative example 3: the difference from example 1 is that the outer layer is not coated with silica particles, only the core layer and the intermediate layer.
Table 1: contact angle of whether 2-acrylamido-2-methylpropanesulfonic acid binder was added.
| Type (B) | Contact angle |
| Example 1 | 155° |
| Comparative example 1 | 138° |
As is clear from the data in Table 1, when 2-acrylamido-2-methylpropanesulfonic acid having a sulfonic acid group was used, the contact angle was significantly increased, and the hydrophobic property was improved.
Table 2: whether or not the coating rate of the epoxy group-containing acrylic resin silica particles is used.
| Type (B) | Coating rate |
| Example 1 | 15.3％ |
| Comparative example 2 | 4.5％ |
The coating rate is calculated by respectively carrying out the above reactions by using glycidyl methacrylate and methacrylate with the same ratio, then respectively coating the silicon dioxide particles on the materials with the same fixed mass and using different acrylic resins, calculating the coated weight after film forming, and dividing the coated weight by the total mass to obtain the coating rate.
As is clear from the data in Table 2, the coating ratio of the silica particles was significantly higher when glycidyl methacrylate was used, indicating that the degree of bonding of the silica particles was better when the acrylic resin having an epoxy group was used.
Table 3: the contact angle of the binder when coated with silica particles.
| Type (B) | Contact angle |
| Example 1 | 155° |
| Comparative example 3 | 120° |
As can be seen from the data in table 3, the coating with silica particles provides a rough surface, which is more hydrophobic than a surface not coated with silica particles.
Claims (3)
1. The aqueous polyurethane acrylate printing adhesive comprises a solvent and polymer particles, and is characterized in that the solvent comprises deionized water, the polymer particles are of a three-layer structure comprising a core layer, a middle layer and a hydrophobic layer, the core layer is aqueous polyurethane, the middle layer is a fluorine-containing acrylate layer, the hydrophobic layer is a silica particle layer, the aqueous polyurethane in the core layer and the fluorine-containing acrylate in the middle layer are mutually combined through sulfonic acid groups and hydroxyl groups in a cross-linking manner, and the fluorine-containing acrylate in the middle layer and the silica particles in the hydrophobic layer are mutually combined through an epoxy ring-opening reaction;
the core layer preparation comprises the following components in parts by mass: 50-70 parts of water, 15-25 parts of a first monomer composition, 0.5-1.5 parts of 1, 4-butanediol, 0.1-0.5 part of dimethylolpropionic acid, 0.3-0.8 part of dibutyltin dilaurate, 1-3 parts of a salt forming agent and 1-5 parts of a terminated monomer;
the intermediate layer comprises the following components in parts by mass: 50-60 parts of N, N-dimethylacetamide, 20-35 parts of a second monomer composition, 0.1-0.3 part of azobisisobutyronitrile, 3-10 parts of glycidyl methacrylate and 0.5-1 part of a crosslinking agent;
the hydrophobic layer comprises the following components in parts by mass: 90-98 parts of 90-97wt% ethanol aqueous solution, 4-8 parts of gamma-aminopropyltriethoxysilane, 2-4 parts of silicon dioxide particles and 1-3 parts of diethylamine;
the first monomer composition in the core layer comprises the following components in parts by mass: 40-60 parts of polytetrahydrofuran ether glycol, 30-40 parts of isophorone diisocyanate and 10-20 parts of polydimethylsiloxane;
the salt forming agent in the nuclear layer is triethylamine, diethylamine or ammonia water;
the end-capping monomer in the core layer is hydroxyethyl methacrylate;
the second monomer composition in the middle layer comprises the following components in parts by mass: 30-40 parts of perfluorohexyl ethyl acrylate, 35-45 parts of methyl methacrylate and 20-30 parts of 2-acrylamide-2-methylpropanesulfonic acid;
the cross-linking agent in the middle layer is methylated hexamethylol melamine.
2. The aqueous polyurethane acrylate printing adhesive according to claim 1, wherein the silica particles in the hydrophobic layer are mesoporous silica particles.
3. The aqueous polyurethane acrylate printing adhesive of claim 1, wherein the silica particles in the hydrophobic layer are nano silica particles.
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| CN103666344A (en) * | 2013-12-06 | 2014-03-26 | 华南理工大学 | Preparation method for high-temperature steaming/boiling resistant composite adhesive for flexible packaging membranes |
| US9074036B1 (en) * | 2014-05-30 | 2015-07-07 | Champward Chemical Industrial Co., Ltd. | Preparing method for aqueous emulsion via dispersible urethane acrylate copolymerization |
| CN105255348A (en) * | 2015-10-13 | 2016-01-20 | 厦门大学 | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101270225A (en) * | 2008-04-30 | 2008-09-24 | 武汉理工大学 | Method for preparing binary dispersion composite emulsion of polyurethane acrylic acid |
| CN102924664A (en) * | 2012-11-20 | 2013-02-13 | 江苏日出化工有限公司 | Preparation method for core-shell fluorinated polyurethane-acrylate latex |
| CN103666344A (en) * | 2013-12-06 | 2014-03-26 | 华南理工大学 | Preparation method for high-temperature steaming/boiling resistant composite adhesive for flexible packaging membranes |
| US9074036B1 (en) * | 2014-05-30 | 2015-07-07 | Champward Chemical Industrial Co., Ltd. | Preparing method for aqueous emulsion via dispersible urethane acrylate copolymerization |
| CN105255348A (en) * | 2015-10-13 | 2016-01-20 | 厦门大学 | One-component transparent waterborne polyurethane emulsion waterproof paint and preparation method thereof |
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