CN111394023B - Water-whitening-resistant acrylate pressure-sensitive adhesive and preparation method thereof - Google Patents
Water-whitening-resistant acrylate pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN111394023B CN111394023B CN202010251894.7A CN202010251894A CN111394023B CN 111394023 B CN111394023 B CN 111394023B CN 202010251894 A CN202010251894 A CN 202010251894A CN 111394023 B CN111394023 B CN 111394023B
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 100
- 239000003999 initiator Substances 0.000 claims abstract description 95
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 35
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 35
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 34
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 26
- WFVZQYQWGBYJRH-UHFFFAOYSA-N but-1-ene;2-methylprop-2-enamide;urea Chemical compound CCC=C.NC(N)=O.CC(=C)C(N)=O WFVZQYQWGBYJRH-UHFFFAOYSA-N 0.000 claims description 22
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 230000002087 whitening effect Effects 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 150000003254 radicals Chemical group 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 101
- 239000000839 emulsion Substances 0.000 description 92
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 69
- 239000008367 deionised water Substances 0.000 description 65
- 229910021641 deionized water Inorganic materials 0.000 description 65
- 238000002156 mixing Methods 0.000 description 48
- 229910052757 nitrogen Inorganic materials 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 31
- 238000003756 stirring Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 238000004945 emulsification Methods 0.000 description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 description 17
- 238000009736 wetting Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QFXBYZKQOKCTQA-UHFFFAOYSA-N (carbamoylamino) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ONC(N)=O QFXBYZKQOKCTQA-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 3
- 239000002313 adhesive film Substances 0.000 description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- AJUIEYXPANEMOX-UHFFFAOYSA-N (carbamoylamino) prop-2-enoate Chemical compound NC(=O)NOC(=O)C=C AJUIEYXPANEMOX-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BNYNKTQCULIVRI-UHFFFAOYSA-N n-but-3-enylprop-2-enamide;urea Chemical compound NC(N)=O.C=CCCNC(=O)C=C BNYNKTQCULIVRI-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a preparation method of a pressure-sensitive adhesive, in particular to an acrylate pressure-sensitive adhesive with good water-white resistance and excellent cohesive strength, which comprises 4-15 parts of hard monomer; 60-90 parts of soft monomer; 3-18 parts of a functional monomer; 1.5-4 parts of emulsifier and 0.1-2 parts of initiator. The invention provides a water-white resistant acrylate pressure-sensitive adhesive with good initial adhesion and cohesive strength, which has excellent water-white resistance and good adhesive property by optimizing and adjusting the proportion of various monomers, introducing new carbamido functional monomers, changing the types of emulsifiers, adding a cross-linking agent and the like in the synthesis process.
Description
Technical Field
The invention relates to a preparation method of a pressure-sensitive adhesive, in particular to an acrylate pressure-sensitive adhesive with good water-whitening resistance and excellent cohesive strength.
Background
Currently, acrylate polymers obtained by copolymerizing a variety of acrylate monomers are an important class of pressure sensitive adhesives. In recent years, due to rapid development in packaging, transportation, materials, and the like, demand for label-type products has been expanding, and thus, demand for pressure-sensitive adhesive products has been expanding. The acrylic pressure-sensitive adhesive emulsion has the characteristics of safety and environmental protection, such as no toxicity, no pollution and the like, and has excellent aging resistance, weather resistance, pressure-sensitive property and adhesiveness, so that the pressure-sensitive adhesive product is widely applied.
Through years of development, the polymerization formula and the polymerization process of the acrylate pressure-sensitive adhesive product are continuously adjusted, and various functional monomers are introduced while the soft monomers and the hard monomers of the acrylate are selected, so that the performance of the acrylate pressure-sensitive adhesive is improved. Nevertheless, acrylate pressure sensitive adhesive emulsions are inferior to solvent-based products in terms of adhesion, high temperature resistance, water-white resistance, moisture resistance, etc.
The pressure-sensitive adhesive emulsion product can be whitened after contacting with water, because water molecules form a water pocket in the gaps of the adhesive layer when diffusing from the outside to the emulsion layer, osmotic pressure is generated to act on latex particles, and light irradiates the water pocket to generate light scattering, so that the water whitening phenomenon is caused. The acrylate pressure sensitive adhesive emulsion is synthesized by an emulsion polymerization method, and most of surfactants, initiators, buffers and the like involved in the process are water-soluble. In the process of drying the emulsion to form a film, the charged particles and the water-soluble components in the emulsion can provide driving force for the adhesive film, so that water molecules can easily act with the components from the outside after the product meets water to generate a casting film sensitive to water, the adhesive film is milky, and when the water temperature is high, the water whitening degree is higher, so that the appearance and the adhesive performance are influenced. For products needing to be stored under low-temperature and humid conditions, such as transparent food packages of beverage bottles and the like, in the process of placing at room temperature after low-temperature storage, water in the air is liquefied when encountering a bottle body and adheres to the wall of the bottle to contact with an adhesive film, so that the water-white problem is caused.
The water-white problem of pressure-sensitive adhesives is one of the problems of aqueous pressure-sensitive adhesives which have been widely regarded in recent years, and there are also considerable technical efforts to develop such properties. The emulsion system is improved by the US patent 20060263600A1, the water-white problem is reduced by selecting fatty alcohol polyether and dioctyl sodium sulfosuccinate, and the emulsion system has a certain water-white resistant effect, but the emulsion process is difficult due to the characteristics of the fatty alcohol polyether. U.S. Pat. No. 4, 20050176876, 1 describes the use of core-shell emulsion polymerization and the incorporation of fluoromonomers to solve the problem of water-white resistance, but also the problem of mechanical properties degradation. Therefore, it is still one of the technical problems in the industry to solve the problems of water-whitening resistance and adhesion performance at the same time.
Disclosure of Invention
Aiming at the situation, the invention provides a water-white-resistant acrylate pressure-sensitive adhesive which is prepared from the following raw materials in parts by weight: 4-15 parts of a hard monomer; 60-90 parts of soft monomer; 3-18 parts of a functional monomer; 1.5-4 parts of emulsifier and 0.1-2 parts of initiator;
as an embodiment of the present invention, the functional monomer comprises a ureido monomer.
As an embodiment of the present invention, the ureido monomer is one selected from the group consisting of acrylamidoethyl ethylene urea, ureido methacrylate, allophanate-modified (cyclo) aliphatic polyisocyanates, and prepolymers thereof.
As an embodiment of the present invention, the homopolymer of the hard monomer is a homopolymer having a glass transition temperature of greater than 10 degrees celsius.
In one embodiment of the present invention, the hard monomer is one or more selected from methyl acrylate, methyl methacrylate, styrene, vinyl acetate, and acrylonitrile.
As an embodiment of the present invention, the homopolymer of the soft monomer is a homopolymer having a glass transition temperature of less than 0 ℃.
As an embodiment of the invention, the soft monomer is selected from one or more of ethyl acrylate, butyl acrylate and isooctyl acrylate.
As an embodiment of the present invention, the initiator is a radical type initiator.
In one embodiment of the present invention, the initiator is potassium persulfate or sodium persulfate.
As an embodiment of the present invention, the emulsifier is selected from one or more of sodium dodecylbenzene sulfonate, sodium lauryl sulfate, modified fatty alcohol polyether, and dioctyl sodium sulfosuccinate.
Has the advantages that: the invention provides a water-white resistant acrylate pressure-sensitive adhesive with good initial adhesion and cohesive strength, which has excellent water-white resistance and good adhesive property by optimizing and adjusting the proportion of various monomers, introducing new carbamido functional monomers, changing the types of emulsifiers, adding a cross-linking agent and the like in the synthesis process.
Detailed Description
The present invention will be described in more detail with reference to the following examples. The technical solutions in the embodiments of the present invention are clearly described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The embodiment provides a water-white resistant acrylate pressure-sensitive adhesive which comprises the following preparation raw materials in parts by weight: 4-15 parts of a hard monomer; 60-90 parts of soft monomer; 3-18 parts of a functional monomer; 1.5-4 parts of emulsifier and 0.1-2 parts of initiator.
The acrylate pressure-sensitive adhesive is a self-adhesive substance, and can form firmer adhesive force under smaller acting force; the adhesive is an adhesive which can be tightly adhered to an adherend by applying light finger pressure without the aid of solvents, heat or other means.
The addition of the hard monomer can increase the cohesive energy of the polymer and improve the cohesive force of the polymer, and the homopolymer of the hard monomer added in the invention is a homopolymer with the glass transition temperature of more than 10 ℃ according to the application environment requirement of the product.
From the polymer perspective, the hard monomer is a hard monomer containing a carbon-carbon double bond.
In one embodiment of the present invention, the hard monomer is one or more selected from methyl acrylate, methyl methacrylate, styrene, vinyl acetate, and acrylonitrile.
The addition of soft monomers can impart adhesion, i.e., tack, to the polymer. From the aspect of improving the initial viscosity of the pressure-sensitive adhesive, the homopolymer of the soft monomer added in the invention is a homopolymer with the glass transition temperature of less than 0 ℃.
As an embodiment of the invention, the soft monomer is selected from one or more of ethyl acrylate, butyl acrylate and isooctyl acrylate.
The content of the functional monomer in the acrylic polymer is often less, but the performance endowed by the functional monomer is often more important, such as improving the mechanical property of film formation, and even making up the defects of soft and hard monomers; improving compatibility, etc.
From the viewpoint of improving initial adhesion and peel strength of the product, the functional monomer is one or more selected from acrylic acid, methacrylic acid, hydroxypropyl acrylate, hydroxypropyl methacrylate, ureido acrylate and acrylamide.
The functional monomer also includes a ureido monomer, from the viewpoint of improving the water-whitening resistance of the product.
Because the carbamido monomer contains double bonds, amino groups, and functional groups such as nitrogen heterocyclic groups of ethylene urea, the stability and water resistance of the emulsion can be enhanced by introducing a small amount of carbamido monomer, crosslinking can be generated in the later synthesis and film forming processes, and the pressure-sensitive adhesive is enhanced, so that the pressure-sensitive adhesive has excellent water-white resistance and adhesive property.
As an embodiment of the present invention, the ureido monomer includes, but is not limited to, one of methacrylamide ethyl ethylene urea, ureido methacrylate, allophanate modified (cyclo) aliphatic polyisocyanates or prepolymers thereof.
The water-resistant white acrylate pressure-sensitive adhesive prepared by the invention adopts an emulsion polymerization mode, and adopts a mode that an emulsifier is used as two emulsifiers for polymerization.
Preferably, the emulsifier is selected from two of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, modified fatty alcohol polyether and dioctyl sodium sulfosuccinate.
In the invention, the initiator is a free radical type initiator, and is specifically potassium persulfate or sodium persulfate.
The second aspect of the invention provides a preparation process of the pressure-sensitive adhesive, which comprises the following steps:
adding a surfactant, a hard monomer, a soft monomer and a functional monomer according to a formula ratio, stirring until emulsification is carried out to prepare a pre-emulsion, taking 10-20% of the pre-emulsion as seeds, adding the seeds when a reaction kettle is heated to 81 ℃ (nitrogen is introduced and exhausted), adding 30-40% of an initiator into the reaction kettle, closing nitrogen, heating to a peak value, simultaneously dropwise adding the rest of the pre-emulsion and the initiator at a constant speed for 4-5h, wherein the reaction temperature is 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to be 6-8 by adding ammonia water, and adding a cross-linking agent, a wetting agent and the like. The films were then tested for water-whitening resistance, initial tack, and peel strength.
The invention relates to a test method which comprises the following steps:
and (3) testing initial adhesion: and (4) testing by using an initial adhesion tester by referring to GB/T4852-2002.
180 ° peel strength: the test is carried out by a universal tester according to the test of GB/T2792-1998.
And (3) testing water resistance: measured with reference to ASTM D1003-00. Preparing a film by using a 40-micron wire rod, and drying the film in a 120-DEG C drying oven to constant weight. And (5) cooling to room temperature, putting one side of the prepared pressure-sensitive adhesive film into deionized water, and measuring the time (h) from water contact to tape whitening.
Has the advantages that: according to the invention, the carbamido monomer is added through the selection of the formula, and crosslinking can be generated in the later synthesis and film forming processes, so that the pressure-sensitive adhesive is increased in adhesiveness, and the pressure-sensitive adhesive has excellent water-white resistance and adhesive property. The prepared pressure-sensitive adhesive has excellent water-white resistance; however, in practical use, the water-whitening resistance, initial tack and cohesion of the product are still not as good as the ideal performance of the product when the carbamido monomer is added. The applicants have discovered, surprisingly, that the emulsifiers are adjusted to DS-4 and SLS; meanwhile, the preparation method of adding DS-4 step by step can prepare the pressure-sensitive adhesive with excellent initial viscosity, cohesive force and water-white resistance.
The following is a detailed description of specific embodiments.
The first embodiment is as follows:
selecting 45 parts of isooctyl acrylate and 43 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 2 parts of acrylic acid as functional monomer; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Uniformly mixing 2 parts of emulsifier and 30 parts of deionized water, and mixing and stirring 45 parts of isooctyl acrylate, 43 parts of butyl acrylate, 10 parts of styrene and 2 parts of acrylic acid with an aqueous solution until emulsification is carried out to obtain the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting to 53.70% of solid content.
Example two:
selecting 42 parts of isooctyl acrylate and 41 parts of butyl acrylate as soft monomers; 15 parts of styrene as hard monomer; 2 parts of acrylic acid as functional monomer; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Uniformly mixing 2 parts of emulsifier and 30 parts of deionized water, and mixing and stirring 42 parts of isooctyl acrylate, 41 parts of butyl acrylate, 15 parts of styrene and 2 parts of acrylic acid with an aqueous solution until emulsification is carried out to obtain a pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.66%.
Example three:
selecting 42 parts of isooctyl acrylate and 36 parts of butyl acrylate as soft monomers; 20 parts of styrene as hard monomer; 2 parts of acrylic acid as functional monomer; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Uniformly mixing 2 parts of emulsifier and 30 parts of deionized water, and mixing and stirring 42 parts of isooctyl acrylate, 36 parts of butyl acrylate, 20 parts of styrene and 2 parts of acrylic acid with an aqueous solution until emulsification is carried out to obtain a pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting to 53.63% of solid content.
Example four:
selecting 52 parts of isooctyl acrylate and 36 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 2 parts of acrylic acid as functional monomer; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 52 parts of isooctyl acrylate, 36 parts of butyl acrylate, 10 parts of styrene and 2 parts of acrylic acid with an aqueous solution, stirring until emulsification is carried out, and thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting to 53.81% of solid content.
Example five:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10.5 parts of styrene as hard monomer; 1.5 parts of acrylic acid and 2 parts of hydroxypropyl acrylate as functional monomers; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10.5 parts of styrene, 1.5 parts of acrylic acid and 2 parts of hydroxypropyl acrylate with the water solution, stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.77 percent.
Example six:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of ureido methacrylate as functional monomers; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of ureido methacrylate with the aqueous solution, stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting to 53.75% of solid content.
Example seven:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.80 percent.
Example eight:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 1 part of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting.
Example nine:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 2 parts of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of ammonium persulfate is taken as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting.
Example ten:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of potassium persulfate as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.80 percent.
Example eleven:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.2 part of potassium persulfate as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.79 percent.
Example twelve:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.8 part of potassium persulfate as an initiator; 2 parts of DS-4 as an emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of emulsifier are taken from the reaction kettle and are uniformly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting to 53.81% of solid content.
Example thirteen:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of potassium persulfate as initiator: 2 parts of SLS as emulsifier.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of DS-4 are taken from the reaction kettle and evenly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. Adjusting the pH value of the emulsion to 6 by adding ammonia water, adding OT-75, stirring for 60mins, and adjusting the wetting to 53.84% of solid content.
Example fourteen:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of potassium persulfate as an initiator; 1 part of DS-4 and 1.5 parts of SLS are taken as emulsifiers.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water and 0.2 part of DS-4 are taken from the reaction kettle and evenly mixed, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.82%.
Example fifteen:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of potassium persulfate as an initiator; 1 part of Disponil AFX-1080 and 1.5 parts of OT-75 as emulsifiers.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water is taken out of the reaction kettle, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. Taking 10% of pre-emulsion as seed emulsion, adding seeds when the temperature of a reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, dropwise adding the rest pre-emulsion and the initiator at a constant speed when the temperature is raised to a peak value, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.80 percent.
Example sixteen:
selecting 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate as soft monomers; 10 parts of styrene as hard monomer; 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea as functional monomers; 0.4 part of potassium persulfate as an initiator; 1 part of DS-4 and 1.5 parts of SLS are taken as emulsifiers.
Mixing 2 parts of emulsifier and 30 parts of deionized water uniformly, mixing 50 parts of isooctyl acrylate, 35.5 parts of butyl acrylate, 10 parts of styrene, 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea with an aqueous solution, and stirring until emulsification is carried out, thus obtaining the pre-emulsion. 40 parts of deionized water is taken out of the reaction kettle, nitrogen is introduced, and the temperature is raised to 81 ℃.7 parts of deionized water and 60% of initiator are mixed to prepare an initiator aqueous solution. And (3) when the temperature of the reaction kettle is raised to 81 ℃, mixing the rest 40% of initiator with two parts of deionized water, adding the mixture into the reaction kettle, closing nitrogen, when the temperature is raised to a peak value, dropwise adding the rest pre-emulsion and the initiator at a constant speed, and reacting for 4.5 hours at a reaction temperature of 85-87 ℃. After the reaction is finished, maintaining the reaction temperature and keeping the temperature for 90mins, then carrying out post-treatment, wherein the post-treatment temperature is 87 ℃, the dripping time is 45mins, keeping the temperature for 15mins, and cooling to the room temperature. The pH value of the emulsion is adjusted to 6 by adding ammonia water, OT-75 is added, the mixture is stirred for 60mins, and the wetting is adjusted to reach the solid content of 53.85 percent.
Through a plurality of experiments, the experimental results of the above examples are as follows:
the invention has the advantages that: the water-whitening-resistant acrylate pressure-sensitive adhesive with good bonding strength disclosed by the invention can simultaneously meet the requirements of required bonding performance and water whitening resistance. The above disclosure is only a few specific embodiments of the present invention, but the present invention is not limited thereto, and any technical changes by those skilled in the art based on the present invention should fall within the scope of the present invention.
Claims (3)
1. The water-whitening-resistant acrylate pressure-sensitive adhesive is characterized by comprising the following preparation raw materials in parts by weight: 10 parts of hard monomer; 85.5 parts of soft monomer; 4 parts of functional monomer; 2.5 parts of emulsifier and 0.4 part of initiator; the functional monomer comprises 1.5 parts of acrylic acid, 2 parts of hydroxypropyl acrylate and 0.5 part of methacrylamide ethyl ethylene urea; the soft monomer comprises 50 parts of isooctyl acrylate and 35.5 parts of butyl acrylate; the hard monomer is 10 parts of styrene; the emulsifier comprises 1 part of DS-4 and 1.5 parts of SLS.
2. The water whitening resistant acrylate pressure sensitive adhesive of claim 1, wherein the initiator is a free radical type initiator.
3. The water-white resistant acrylate pressure sensitive adhesive of claim 2 wherein the initiator is potassium persulfate or sodium persulfate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010251894.7A CN111394023B (en) | 2020-04-01 | 2020-04-01 | Water-whitening-resistant acrylate pressure-sensitive adhesive and preparation method thereof |
| PCT/CN2021/081160 WO2021197054A1 (en) | 2020-04-01 | 2021-03-16 | Water-white-resistant acrylate pressure-sensitive adhesive and preparation method therefor |
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| CN202010251894.7A CN111394023B (en) | 2020-04-01 | 2020-04-01 | Water-whitening-resistant acrylate pressure-sensitive adhesive and preparation method thereof |
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