CN109295766A - A kind of aqueous polyurethane acrylate printing adhesive - Google Patents
A kind of aqueous polyurethane acrylate printing adhesive Download PDFInfo
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- CN109295766A CN109295766A CN201811174534.0A CN201811174534A CN109295766A CN 109295766 A CN109295766 A CN 109295766A CN 201811174534 A CN201811174534 A CN 201811174534A CN 109295766 A CN109295766 A CN 109295766A
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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
-
- 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
-
- 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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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of pigment printing binding agents, more particularly to a kind of aqueous polyurethane acrylate printing adhesive, including solvent and polymer beads, the solvent includes deionized water, the polymer beads are stratum nucleare, middle layer and hydrophobic layer three-decker, it is aqueous polyurethane in the stratum nucleare, the middle layer is fluorine-containing ester layer, the hydrophobic layer is silicon dioxide granule layer, aqueous polyurethane is crosslinked with hydroxyl by sulfonic group with middle layer fluorinated acrylate and is be combined with each other in the stratum nucleare, silicon dioxide granule in middle layer fluorinated acrylate and hydrophobic layer is be combined with each other by epoxy ring opening reaction, flexibility of the present invention is good, combine dynamics larger between each layer, and using fluorinated acrylate and rough surface is constituted using silicon dioxide granule, with preferable hydrophobic performance.
Description
Technical field
The present invention relates to a kind of pigment printing binding agent more particularly to a kind of aqueous polyurethane acrylate printed adhesives
Agent.
Background technique
Acrylic ester adhesive, due to the plurality of advantages that it has, such as adhesive property height, curing rate is fast, extensive suitable
Ying Xing, excellent in mechanical performance and to bonding object non-selectivity etc. are greatly paid close attention to, but also expose many scarce since then
It falls into, glue film is tacky, and water resistance and temperature tolerance are bad, and penetrability and gas permeability are poor, anti-after-tackiness when film formation at low temp, high temperature
Bad, elongation percentage is relatively low.For these problems, many study on the modification are carried out to the structure of such adhesive, but big
Partial study on the modification can improve the property such as water resistance, temperature tolerance and elongation at break all just for some defect simultaneously
The research of energy is seldom.The water resistance and adhesiveness that water-based polyurethane adhesive has are good, and for emulsion-stabilizing without precipitating, glue film is mechanical
The advantages that performance is good, tack-free, the shortcomings that effectively compensating for acrylate adhesive, but the cost of aqueous polyurethane adhesive
It is higher, therefore the production cost of adhesive can be effectively reduced in use acrylic ester modified water-soluble polyurethane, and can be simultaneously by two
The performance of kind adhesive combines, also, hydrophobic stain resistance is also an important indicator after adhesive film forming, the prior art
In often simply by fluoro-containing group is introduced in adhesive, reduce adhesive surface energy, but due to adhesive at film thickness compared with
Be it is smooth, cause this method promoted hydrophobicity it is limited.
Patent Office of the People's Republic of China discloses a kind of preparation method of acrylic ester modified water-soluble polyurethane on December 5th, 2012
Patent of invention, Authorization Notice No. CN102807664A, the present invention provides a kind of systems of acrylic ester modified water-soluble polyurethane
Preparation Method belongs to technical field of polymer materials.The material is the poly- ammonia of acrylic ester modified water-soluble that main chain introduces activity double key
Ester, this method introduces activity double key using butylene glycol as chain extender on polyurethane molecular main chain, main in polyurethane chain
Activity double key is introduced, then polyurethane backbone is linked together by double-bond polymerization with acrylate monomer again, is formed netted
Structure, to synthesize acrylate modified aqueous polyurethane product.Synthetic method of the invention is simple, is easy to implement, and produces
Moral character can it is good, low in cost, production and use during do not generate pollution, have in coating, adhesive, synthetic leather industry
Broad application prospect, but the proprietary material surface does not have hydrophobicity, can not provide long-term waterproof, prevents dirty, anti-corrosion
The characteristics such as erosion.
Summary of the invention
The problems such as acrylic polymer hydrophobic performance is poor in the prior art for solution, and after tack is bad, and feel is stiff,
Propose a kind of with three-decker, the aqueous polyurethane acrylate printing adhesive with super-hydrophobicity.
To achieve the above object, the invention adopts the following technical scheme:
A kind of aqueous polyurethane acrylate printing adhesive, including solvent and polymer beads, the solvent include deionization
Water, the polymer beads are stratum nucleare, middle layer and hydrophobic layer three-decker, are aqueous polyurethane in the stratum nucleare, it is described in
Interbed is fluorine-containing ester layer, and the hydrophobic layer is silicon dioxide granule layer, aqueous polyurethane and middle layer in the stratum nucleare
Fluorinated acrylate is crosslinked with hydroxyl by sulfonic group and is be combined with each other, the titanium dioxide in middle layer fluorinated acrylate and hydrophobic layer
Silicon particle is be combined with each other by epoxy ring opening reaction.
The aqueous polyurethane acrylate printing adhesive sent out in the invention patent includes aqueous solvent and polymer beads, is gathered
Polymer beads include stratum nucleare, middle layer and hydrophobic layer three-decker, and wherein stratum nucleare is aqueous polyurethane layer, and aqueous polyurethane has
The features such as flexibility is good, low temperature resistant, adhesion strength is strong, middle layer are acrylate resin layer, include sulfonic group in interlayer component
The sum of group is comprising containing epoxy group, after sulfonic acid group is by adding suitable crosslinking agent, can in stratum nucleare aqueous polyurethane
Hydroxyl crosslink reaction, considerably increase the cladding power of middle layer and stratum nucleare, and hydrophilic radical can also be inhibited to surface
It migrates, cooperates the low-surface-energy of fluoro-containing group, greatly increase material surface hydrophobicity；Hydrophobic layer is silicon dioxide granule cladding
Layer, silicon dioxide granule to form chemical bond and are coated on polymer particle surface with reacting in middle layer containing epoxy group, formation
Coarse structure surface, considerably increases material hydrophobic.
Preferably, the stratum nucleare preparation includes the quality proportioning of following components and each component are as follows: 50-70 parts of water, first
15-25 parts of monomer composition, 0.5-1.5 parts of 1,4-butanediol, double hydroxymethyl propionic acid 0.1-0.5 parts, dibutyl tin dilaurate
0.3-0.8 parts, 1-3 parts of salt forming agent, 1-5 parts of capping monomer；The middle layer preparation includes the quality of following components and each component
Proportion are as follows: 50-60 parts of N, N- dimethylacetamide ammonia, 20-35 parts of second comonomer composition, 0.1-0.3 parts of azodiisobutyronitrile, first
3-10 parts of base glycidyl acrylate, 0.5-1 parts of crosslinking agent；The hydrophobic layer includes that the quality of following components and each component is matched
Than are as follows: 90-98 parts of 90-97wt% ethanol water, 4-8 parts of gamma-aminopropyl-triethoxy-silane, 2-4 parts of silicon dioxide granule,
1-3 parts of diethylamine.
The glycidyl methacrylate containing epoxy group is introduced, the cladding of improved silica is conducive to.
Preferably, the first monomer composition includes the quality proportioning of following components and each component in the stratum nucleare are as follows: poly-
40-60 parts of tetrahydrofuran ether glycol, 30-40 parts of isophorone diisocyanate, 10-20 parts of dimethyl silicone polymer.
Preferably, salt forming agent is triethylamine, diethylamine or ammonium hydroxide in the stratum nucleare.
Salt forming agent is reacted with isocyano, neutralization reaction system, so that the presence that polyaminoester emulsion is more stable.
Preferably, capping monomer is hydroxyethyl methacrylate in the stratum nucleare.
Hydroxyethyl methacrylate is used to react with the isocyano in aqueous polyurethane, for introducing double bond.
Preferably, second comonomer composition includes the quality proportioning of following components and each component in the middle layer are as follows:
30-40 parts of perfluoro hexyl ethyl propylene acid esters, 35-45 parts of methyl methacrylate, -2 methyl propane sulfonic acid 20-30 of 2- acrylamide
Part.
- 2 methyl propane sulfonic acid of 2- acrylamide with sulfonic acid group is used in middle layer monomer, sulfonic acid group can be with
Hydroxyl crosslinking in aqueous polyurethane, increases binding force, and can prevent hydrophilic radical from migrating to surface, and middle layer monomer is also
Using fluorochemical monomer perfluoro hexyl ethyl propylene acid esters, low-surface-energy is dropped, hydrophobicity is further increased.
Preferably, crosslinking agent is methyl-etherified hexamethylolmelamine in the middle layer.
Methyl-etherified hexamethylolmelamine can promote sulfonic acid group and hydroxyl to crosslink.
Preferably, silicon dioxide granule described in the hydrophobic layer is meso-porous titanium dioxide silicon particle.
Preferably, silicon dioxide granule described in the hydrophobic layer is nano-silicon dioxide particle.
Advantageous effect of the invention is: (1) polymer beads are three-decker in printing adhesive of the invention, and stratum nucleare is
Aqueous polyurethane, flexibility are good；(2) middle layer is the fluorine-containing ester layer with sulfonic acid group and epoxy group, sulfonic group
Group can be crosslinked with the hydroxyl in stratum nucleare aqueous polyurethane, increase cladding dynamics, epoxy group can be with outer layer amination silica
Particle reaction combines；(3) polymer beads outermost layer is coated with silicon oxide particle, increases adhesive surface roughness, ties
The characteristic that middle layer fluoro-containing group surface can be low is closed, provides preferable hydrophobic performance for material.
Specific embodiment
The present invention program is more clearly and completely described below in conjunction with specific embodiment, it is clear that described implementation
Example is only a part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
Embodiment 1: aqueous polyurethane acrylate printing adhesive preparation step is as follows:
(1) polytetrahydrofuran ether glycol is put into 70 DEG C of dehydration deoxygenation 1h in drying box；
(2) the first monomer composition of 50g is added in 200g deionized water, the first monomer composition quality proportioning is poly- four
40 parts of glycol of hydrogen furans ether, 50 parts of isophorone diisocyanate, 10 parts of dimethyl silicone polymer, 3.2g1,4- fourth is then added
The bis- hydroxymethyl propionic acids of glycol, 0.8g, 1.5g dibutyl tin dilaurate, argon gas protection, react 1.2h at 60 DEG C, obtain poly- ammonia
Ester prepolymer；
(3) 3.2g hydroxyethyl methacrylate is added in polyurethane prepolymer, reacts 0.5h at 60 DEG C, it is poly- to obtain double bond sealing end
Urethane；
(4) diethylamine aqueous solution that 15g degree of neutralization is 90% is added, obtains aqueous polyurethane；
(5) 65g second comonomer composition is added in 150gN, N- dimethylacetamide ammonia, the second comonomer composition quality is matched
Than are as follows: 30 parts of perfluoro hexyl ethyl propylene acid esters, 45 parts of methyl methacrylate, 25 parts of -2 methyl propane sulfonic acid of 2- acrylamide,
After being sufficiently mixed, under protection of argon gas, 0.52g azodiisobutyronitrile is added, then reacts 8h at 60 DEG C, is then poured into dialysis
Bag dialysis 5 days is freeze-dried 20h at -50 DEG C and obtains emulsifier；
(6) 50g emulsifier and 10g glycidyl methacrylate are added in aqueous polyurethane obtained by step (4), are added
0.13g azodiisobutyronitrile and 1.3g methyl-etherified hexamethylolmelamine, obtain aqueous polyurethane acrylate lotion；
(7) 2g silicon dioxide granule is dissolved in the 95wt% ethanol water of 20g, ultrasonic disperse 30min；
(8) diethylamine is added dropwise and pH is adjusted to 8.5；
(9) 5g gamma-aminopropyl-triethoxy-silane is added dropwise dropwise in silica ethanol solution, reacts 5h at 75 DEG C；
(10) it filters and obtains modified silicon dioxide granule, then use modified silicon dioxide granule the ethanol water of 95wt%
Solution washing obtains amination silicon dioxide granule after 100 DEG C of drying；
(11) the modified silicon dioxide granule of 2g gamma-aminopropyl-triethoxy-silane is added in gained lotion in step (6), adds
Enter 5g diethylamine, aqueous polyurethane acrylate printing adhesive is prepared to being completely dissolved in magnetic agitation at room temperature.
Embodiment 2: aqueous polyurethane acrylate printing adhesive preparation step is as follows:
(1) polytetrahydrofuran ether glycol is put into 80 DEG C of dehydration deoxygenation 2h in drying box；
(2) the first monomer composition of 70g is added in 300g deionized water, the first monomer composition quality proportioning is poly- four
50 parts of glycol of hydrogen furans ether, 30 parts of isophorone diisocyanate, 20 parts of dimethyl silicone polymer, 4g1,4- fourth two is then added
The bis- hydroxymethyl propionic acids of alcohol, 1.3g, 2.1g dibutyl tin dilaurate, argon gas protection, react 2h at 70 DEG C, it is pre- to obtain polyurethane
Polymers；
(3) hydroxyethyl methacrylate is added in 4.1g in polyurethane prepolymer, reacts 1h at 70 DEG C, obtains double bond and blocks poly- ammonia
Ester；(4) diethylamine aqueous solution that 40g degree of neutralization is 95% is added, obtains aqueous polyurethane；
(5) 95g second comonomer composition is added in 180gN, N- dimethylacetamide ammonia, the second comonomer composition quality is matched
Than are as follows: 40 parts of perfluoro hexyl ethyl propylene acid esters, 40 parts of methyl methacrylate, 20 parts of -2 methyl propane sulfonic acid of 2- acrylamide,
After being sufficiently mixed, under protection of argon gas, 0.76g azodiisobutyronitrile is added, then reacts 10h at 70 DEG C, is then poured into
It analyses bag to dialyse 8 days, 25h is freeze-dried at -45 DEG C and obtains emulsifier；
(6) 80g emulsifier and 20g glycidyl methacrylate are added in aqueous polyurethane obtained by step (4), are added
0.18g azodiisobutyronitrile and 2.2g methyl-etherified hexamethylolmelamine, obtain aqueous polyurethane acrylate lotion；
(7) 3g silicon dioxide granule is dissolved in the 97wt% ethanol water of 40g, ultrasonic disperse 50min；
(8) diethylamine is added dropwise and pH is adjusted to 8.9；
(9) 7g gamma-aminopropyl-triethoxy-silane is added dropwise dropwise in silica ethanol solution, reacts 5h at 70 DEG C；
(10) it filters and obtains modified silicon dioxide granule, then use modified silicon dioxide granule the ethanol water of 95wt%
Solution washing obtains amination silicon dioxide granule after 110 DEG C of drying；
(11) the modified silicon dioxide granule of 3g gamma-aminopropyl-triethoxy-silane is added in gained lotion in step (6), adds
Enter 5.5g diethylamine, aqueous polyurethane acrylate printing adhesive is prepared to being completely dissolved in magnetic agitation at room temperature.
Embodiment 3: aqueous polyurethane acrylate printing adhesive preparation step is as follows:
(1) polytetrahydrofuran ether glycol is put into 75 DEG C of dehydration deoxygenation 1.5h in drying box；
(2) the first monomer composition of 85g is added in removing 350g ionized water, the first monomer composition quality proportioning is poly- four
60 parts of glycol of hydrogen furans ether, 30 parts of isophorone diisocyanate, 10 parts of dimethyl silicone polymer, 4.6g1,4- fourth is then added
The bis- hydroxymethyl propionic acids of glycol, 3.1g, 2.3g dibutyl tin dilaurate, argon gas protection, react 3h at 80 DEG C, obtain polyurethane
Prepolymer；
(3) 2.1g hydroxyethyl methacrylate is added in polyurethane prepolymer, reacts 1.5h at 80 DEG C, it is poly- to obtain double bond sealing end
Urethane；
(4) diethylamine aqueous solution that 30g degree of neutralization is 98% is added, obtains aqueous polyurethane；
(5) 120g second comonomer composition, the second comonomer composition quality are added in 200gN, N- dimethylacetamide ammonia
Proportion are as follows: 25 parts of perfluoro hexyl ethyl propylene acid esters, 45 parts of methyl methacrylate, -2 methyl propane sulfonic acid 30 of 2- acrylamide
Part, after being sufficiently mixed, under protection of argon gas, 0.96g azodiisobutyronitrile is added, then reacts 12h at 78 DEG C, is then poured into
Bag filter is dialysed 9 days, and 28h is freeze-dried at -50 DEG C and obtains emulsifier；
(6) 110g emulsifier and 30g glycidyl methacrylate are added in aqueous polyurethane obtained by step (4), are added
Enter 0.21g azodiisobutyronitrile and 4g methyl-etherified hexamethylolmelamine, obtains aqueous polyurethane acrylate lotion；
(7) 2.5g silicon dioxide granule is dissolved in the 95wt% ethanol water of 30g, ultrasonic disperse 50min；
(8) diethylamine is added dropwise and pH is adjusted to 9；
(9) 6g gamma-aminopropyl-triethoxy-silane is added dropwise dropwise in silica ethanol solution, reacts 4h at 80 DEG C；
(10) it filters and obtains modified silicon dioxide granule, then use modified silicon dioxide granule the ethanol water of 97wt%
Solution washing obtains amination silicon dioxide granule after 120 DEG C of drying；
(11) the modified silicon dioxide granule of 2.5g gamma-aminopropyl-triethoxy-silane is added in gained lotion in step (6),
5g diethylamine is added, aqueous polyurethane acrylate printing adhesive is prepared to being completely dissolved in magnetic agitation at room temperature.
Comparative example 1: the difference from embodiment 1 is that, second comonomer proportion is perfluoro hexyl ethylacrylic acid in step (5)
40 parts of ester, 60 parts of methyl methacrylate, -2 methyl propane sulfonic acid of 2- acrylamide is not contained, methyl-etherified six is not added in (6) in step
Melamine methylol.
Comparative example 2: the difference from embodiment 1 is that, the glycidyl methacrylate in step (6) changes into without ring
The methacrylate of oxygen groups.
Comparative example 3: the difference from embodiment 1 is that, outer layer is coated without using silicon dioxide granule, only stratum nucleare and centre
Layer.
Table 1: the contact angle of -2 methyl propane sulfonic acid adhesive of 2- acrylamide whether is added.
| Type | Contact angle |
| Embodiment 1 | 155° |
| Comparative example 1 | 138° |
From the data in table 1, it can be seen that after using -2 methyl propane sulfonic acid of 2- acrylamide with sulfonic acid group, on contact angle is obvious
It rises, hydrophobic performance is more preferable.
Table 2: the clad ratio of the acrylic resin silicon dioxide granule of class containing epoxy group whether is used.
| Type | Clad ratio |
| Embodiment 1 | 15.3% |
| Comparative example 2 | 4.5% |
The calculation of clad ratio is the glycidyl methacrylate and methacrylate point using identical proportion
Above-mentioned reaction is not carried out, and titanium dioxide silicon grain then is carried out to the material using different acrylic resins of identical fixed mass respectively
The cladding of son, the weight after cladding is calculated after film forming, obtains clad ratio divided by gross mass for the weight after cladding.
From the data in table 2, it can be seen that after using glycidyl methacrylate, the clad ratio of silicon dioxide granule is obviously more
Height illustrates more preferable using silicon dioxide granule conjugation after band epoxy group class acrylic resin.
Table 3: the contact angle of adhesive when whether being coated using silicon dioxide granule.
| Type | Contact angle |
| Embodiment 1 | 155° |
| Comparative example 3 | 120° |
From the data in table 3, it can be seen that providing rough surface after coating using silicon dioxide granule, compares and silica is not used
The surface of particle cladding, hydrophobicity are more preferable.
Claims (9)
1. a kind of aqueous polyurethane acrylate printing adhesive, including solvent and polymer beads, which is characterized in that described molten
Agent includes deionized water, and it is aqueous poly- in the stratum nucleare that the polymer beads, which are stratum nucleare, middle layer and hydrophobic layer three-decker,
Urethane, the middle layer are fluorine-containing ester layer, and the hydrophobic layer is silicon dioxide granule layer, aqueous poly- ammonia in the stratum nucleare
Ester is crosslinked with hydroxyl by sulfonic group with middle layer fluorinated acrylate and is be combined with each other, middle layer fluorinated acrylate and hydrophobic layer
In silicon dioxide granule be combined with each other by epoxy ring opening reaction.
2. a kind of aqueous polyurethane acrylate printing adhesive according to claim 1, which is characterized in that the stratum nucleare
Preparation includes the quality proportioning of following components and each component are as follows: and 50-70 parts of water, the first 15-25 parts of monomer composition, Isosorbide-5-Nitrae-fourth two
0.5-1.5 parts of alcohol, double hydroxymethyl propionic acid 0.1-0.5 parts, 0.3-0.8 parts of dibutyl tin dilaurate, 1-3 parts of salt forming agent, sealing end
1-5 parts of monomer；
The middle layer preparation includes the quality proportioning of following components and each component are as follows: 50-60 parts of N, N- dimethylacetamide ammonia, the
Two 20-35 parts of monomer compositions, 0.1-0.3 parts of azodiisobutyronitrile, 3-10 parts of glycidyl methacrylate, crosslinking agent
0.5-1 parts；
The hydrophobic layer includes the quality proportioning of following components and each component are as follows: and 90-98 parts of 90-97wt% ethanol water, γ-
4-8 parts of aminopropyl triethoxysilane, 2-4 parts of silicon dioxide granule, 1-3 parts of diethylamine.
3. a kind of aqueous polyurethane acrylate printing adhesive according to claim 2, which is characterized in that the stratum nucleare
In the first monomer composition include following components and each component quality proportioning are as follows: 40-60 parts of polytetrahydrofuran ether glycol, different Buddhist
You have 30-40 parts of ketone diisocyanate, 10-20 parts of dimethyl silicone polymer.
4. a kind of aqueous polyurethane acrylate printing adhesive according to claim 2 or 3, which is characterized in that described
Salt forming agent is triethylamine, diethylamine or ammonium hydroxide in stratum nucleare.
5. a kind of aqueous polyurethane acrylate printing adhesive according to claim 4, which is characterized in that the stratum nucleare
Middle capping monomer is hydroxyethyl methacrylate.
6. a kind of aqueous polyurethane acrylate printing adhesive according to claim 2, which is characterized in that the centre
Second comonomer composition includes the quality proportioning of following components and each component in layer are as follows: perfluoro hexyl ethyl propylene acid esters 30-40
Part, 35-45 parts of methyl methacrylate, 20-30 parts of -2 methyl propane sulfonic acid of 2- acrylamide.
7. a kind of aqueous polyurethane acrylate printing adhesive according to claim 2 or 6, which is characterized in that described
Crosslinking agent is methyl-etherified hexamethylolmelamine in middle layer.
8. a kind of aqueous polyurethane acrylate printing adhesive according to claim 7, which is characterized in that described hydrophobic
Silicon dioxide granule described in layer is meso-porous titanium dioxide silicon particle.
9. a kind of aqueous polyurethane acrylate printing adhesive according to claim 7, which is characterized in that described hydrophobic
Silicon dioxide granule described in layer is nano-silicon dioxide particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811174534.0A CN109295766B (en) | 2018-10-09 | 2018-10-09 | Waterborne polyurethane acrylate printing adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811174534.0A CN109295766B (en) | 2018-10-09 | 2018-10-09 | Waterborne polyurethane acrylate printing adhesive |
Publications (2)
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| CN110467830A (en) * | 2019-07-23 | 2019-11-19 | 北京易净星科技有限公司 | Wear-resisting hydrophobic coating and the method for preparing wear-resisting hydrophobic coating |
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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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| 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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| CN110467830A (en) * | 2019-07-23 | 2019-11-19 | 北京易净星科技有限公司 | Wear-resisting hydrophobic coating and the method for preparing wear-resisting hydrophobic coating |
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