CN113637433A - Water-based acrylate pressure-sensitive adhesive and application thereof - Google Patents
Water-based acrylate pressure-sensitive adhesive and application thereof Download PDFInfo
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- CN113637433A CN113637433A CN202111070558.3A CN202111070558A CN113637433A CN 113637433 A CN113637433 A CN 113637433A CN 202111070558 A CN202111070558 A CN 202111070558A CN 113637433 A CN113637433 A CN 113637433A
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- mass
- sensitive adhesive
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- monomer
- acrylate
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 239000008367 deionised water Substances 0.000 claims abstract description 44
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 8
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000001681 protective effect Effects 0.000 claims description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 14
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 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 10
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- ZBTGXRBMYGTQHK-UHFFFAOYSA-N azanium;2-nonylphenolate Chemical compound N.CCCCCCCCCC1=CC=CC=C1O ZBTGXRBMYGTQHK-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 7
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- SXEQNYJKZGIDTG-UHFFFAOYSA-N n-methoxy-2-methylprop-2-enamide Chemical compound CONC(=O)C(C)=C SXEQNYJKZGIDTG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000000839 emulsion Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000004026 adhesive bonding Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
-
- 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
- C09J133/06—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
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention discloses a water-based acrylate pressure-sensitive adhesive and application thereof, wherein the water-based acrylate pressure-sensitive adhesive comprises a component A and a component B, and the component A comprises the following raw material components in parts by weight: 75-88 parts by mass of a soft monomer, 8-15 parts by mass of a hard monomer, 2-6 parts by mass of a polar monomer, 0.3-2 parts by mass of an internal crosslinking monomer, 0.5-2 parts by mass of an anionic emulsifier, 0.2-1.2 parts by mass of a functional monomer, 0-0.2 part by mass of a buffering agent, 0.3-1 part by mass of an initiator, 80-140 parts by mass of deionized water and 0.5-2 parts by mass of a pH value regulator, wherein the component B comprises a trifunctional aziridine crosslinking agent. The water-based acrylate pressure-sensitive adhesive realizes lower peeling force through the acrylate monomers with two double bonds in the component A, is resistant to humidity and heat, has no residual adhesive ghost, and can greatly improve the production efficiency.
Description
Technical Field
The invention relates to a pressure-sensitive adhesive, in particular to a water-based acrylate pressure-sensitive adhesive and application thereof.
Background
With the continuous improvement of the living standard of people, various household appliances gradually enter thousands of households, and the rapid development of the household appliance industry is driven. The requirement for protecting the electric appliance is higher and higher while the household appliance industry is developed, which is undoubtedly a chance for each large protection film company, but is a great challenge at the same time, the technical requirement of the household appliance protection film is higher, the protection film is not only required to generate glue dropping in the removal process, but also required to reach the conditions of 2000 m/roll without joint, no crystal point in appearance, no impurities, no wrinkles, no offset printing and the like, so that the high requirement is provided for the whole manufacturing process of the household appliance protection film, and the pressure-sensitive adhesive for the household appliance protection film is an important link.
Therefore, there is a need to provide a water-based acrylate pressure-sensitive adhesive to solve the above problems.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a water-based acrylate pressure-sensitive adhesive and application thereof, which can avoid crystal points generated in the process of coating the pressure-sensitive adhesive into a protective film and avoid the problems of adhesive falling, mottling and the like in the process of removing the protective film.
In order to achieve the purpose, the embodiment of the invention provides a water-based acrylate pressure-sensitive adhesive, which comprises a component A and a component B, wherein the component A comprises the following raw material components in parts by weight: 75-88 parts by mass of a soft monomer, 8-15 parts by mass of a hard monomer, 2-6 parts by mass of a polar monomer, 0.3-2 parts by mass of an internal crosslinking monomer, 0.5-2 parts by mass of an anionic emulsifier, 0.2-1.2 parts by mass of a functional monomer, 0-0.2 part by mass of a buffering agent, 0.3-1 part by mass of an initiator, 80-140 parts by mass of deionized water and 0.5-2 parts by mass of a pH value regulator, wherein the component B comprises a trifunctional aziridine crosslinking agent.
In one or more embodiments of the present invention, the soft monomer includes one or more of butyl acrylate, butyl methacrylate, and isooctyl acrylate.
In one or more embodiments of the present invention, the hard monomer includes one or both of methyl acrylate and methyl methacrylate.
In one or more embodiments of the present invention, the polar monomer includes one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, and hydroxypropyl acrylate.
In one or more embodiments of the present invention, the internal crosslinking monomer includes one or more of glycidyl methacrylate, N-methylolacrylamide, and N-methoxymethylacrylamide.
In one or more embodiments of the present invention, the anionic emulsifier includes one or both of ammonium nonylphenol polyoxyethylene ether sulfate and sodium dodecyldiphenyloxide disulfonate.
In one or more embodiments of the present invention, the functional monomer is an acrylate containing two double bonds, and the acrylate containing two double bonds includes one or more of allyl methacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol (400) diacrylate, and tripropylene glycol diacrylate.
In one or more embodiments of the invention, the buffer comprises sodium bicarbonate; the pH value regulator comprises ammonia water.
In one or more embodiments of the invention, the initiator comprises one or both of sodium persulfate and ammonium persulfate.
In one or more embodiments of the invention, the application of the water-based acrylate pressure-sensitive adhesive in the protective film is also provided.
Compared with the prior art, the water-based acrylate pressure-sensitive adhesive provided by the embodiment of the invention has the advantages that through the acrylate monomers with two double bonds in the component A, when emulsion copolymerization is carried out, only one double bond participates in polymerization reaction at the initial stage of the monomers due to the influence of steric hindrance, so that an acrylate polymer with only slight crosslinking is generated, and in the later-stage film forming process, the acrylate polymer is further deeply crosslinked with an additional crosslinking agent under a higher condition to improve the cohesive force, so that the moisture and heat resistance is realized, and no residual gum ghost is caused.
Detailed Description
Specific embodiments of the present invention are described in detail with the understanding that the scope of the present invention is not limited by the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
The water-based acrylate pressure-sensitive adhesive comprises a component A and a component B, wherein the component A comprises the following raw material components in parts by weight: 75-88 parts by mass of a soft monomer, 8-15 parts by mass of a hard monomer, 2-6 parts by mass of a polar monomer, 0.3-2 parts by mass of an internal crosslinking monomer, 0.5-2 parts by mass of an anionic emulsifier, 0.2-1.2 parts by mass of a functional monomer, 0-0.2 part by mass of a buffering agent, 0.3-1 part by mass of an initiator, 80-140 parts by mass of deionized water and 0.5-2 parts by mass of a pH value regulator, wherein the component B comprises a trifunctional aziridine crosslinking agent.
Wherein the soft monomer comprises one or more of butyl acrylate, butyl methacrylate and isooctyl acrylate.
Wherein the hard monomer comprises one or two of methyl acrylate and methyl methacrylate.
Wherein the polar monomer comprises one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate and hydroxypropyl acrylate.
Wherein the internal crosslinking monomer comprises one or more of glycidyl methacrylate, N-methylolacrylamide and N-methoxy methacrylamide.
Wherein the anionic emulsifier comprises one or two of ammonium nonylphenol polyoxyethylene ether sulfate and sodium dodecyl diphenyl ether disulfonate.
The functional monomer is acrylate containing two double bonds, and the acrylate containing two double bonds comprises one or more of allyl methacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol (400) diacrylate and tripropylene glycol diacrylate.
Wherein the buffer comprises sodium bicarbonate; the pH regulator comprises ammonia water.
Wherein, the initiator comprises one or two of sodium persulfate and ammonium persulfate.
The invention also discloses application of the water-based acrylate pressure-sensitive adhesive in a protective film.
The preparation of component A is described in detail below:
(1) weighing all the anionic emulsifier and 30 parts by mass of deionized water, uniformly stirring, adding the soft monomer, the hard monomer, the polar monomer, the internal crosslinking monomer and the functional monomer, and stirring at the speed of 600r/min for 45min to prepare a pre-emulsion;
(2) adding a buffer (or not adding the buffer) and part of deionized water into a reaction kettle, heating to 80-82 ℃, injecting 5-10% of the pre-emulsion and 60% of an initiator, and reacting for 15-20min after a blue phase appears in the system;
(3) after the reaction is finished, beginning to dropwise add the residual pre-emulsion and the initiator at 80-82 ℃, and dropwise adding for 3.5-4.0 h;
(4) and after the dropwise addition, heating the reaction kettle to 85-88 ℃, reacting for 1.5 hours, cooling to 40 ℃, adding a pH value regulator, regulating the pH value to 7-8, filtering by a 300-mesh sieve, and discharging to obtain the component A.
The preparation of the aqueous acrylate pressure-sensitive adhesive will be described in detail below:
(1) weighing 100g of the component A and a beaker, and stirring;
(2) weighing 0.5-2.0 parts of the component B in a container, adding 4 times of deionized water, and uniformly mixing;
(3) and slowly adding the diluted component B into the component A, and stirring for 15-30 min.
The prepared water-based acrylate pressure-sensitive adhesive has timeliness, namely when the water-based acrylate pressure-sensitive adhesive needs to be coated on a base material during reuse, and when the component A and the component B are mixed to prepare the water-based acrylate pressure-sensitive adhesive.
And coating the prepared water-based acrylate pressure-sensitive adhesive on a required substrate, and heating and drying to obtain the household appliance protective film.
The invention is illustrated in detail below with reference to specific examples:
in the case of the example 1, the following examples are given,
1) weighing 1.2g of ammonium nonylphenol polyoxyethylene ether sulfate and 30g of deionized water, stirring at normal temperature to obtain an emulsifier aqueous solution, adding a mixed monomer consisting of 70g of butyl acrylate, 5g of isooctyl acrylate, 1.2g of hydroxypropyl acrylate, 1g of glycidyl methacrylate, 0.6g of ethylene glycol diacrylate, 0.7g of acrylic acid and 15g of methyl methacrylate, stirring for 45min at a stirring speed of 600r/min to obtain a pre-emulsion;
2) adding 40g of deionized water and 0.1g of sodium bicarbonate into a reaction kettle, heating to 80 ℃, and then injecting 9.31g of pre-emulsion; then dissolving 0.36g of sodium persulfate by 10g of deionized water, adding the sodium persulfate into the reaction kettle when the temperature of the reaction kettle is stabilized at 80 ℃, and reacting for 15min when a blue phase appears in the system;
3) after the reaction is finished, adding 0.24g of sodium persulfate into 30g of deionized water for dissolution to prepare an initiator solution; dropwise adding the rest of pre-emulsion and initiator solution at 80 ℃ for 3.5 h;
4) after the dropwise addition, heating the reaction kettle to 85 ℃, reacting for 1.5 hours, cooling to 40 ℃, adding 1.5g of ammonia water and 10g of deionized water, adjusting the pH value to 7-8, filtering by a 300-mesh sieve, and discharging to obtain the component A.
5) 100g of component A is weighed into a beaker, and stirring is started.
6) 0.5g of the component B (aziridine crosslinking agent SAC-100) is weighed, 4g of deionized water is added, the mixture is stirred uniformly by a glass rod and then added into the component A, and the stirring is continued for 20 min. Coating the prepared pressure-sensitive adhesive on a substrate, and controlling the gluing amount to be 3 +/-1 g/m2And finally obtaining the protective film.
In the case of the example 2, the following examples are given,
1) weighing 1.8g of sodium dodecyl diphenyl ether disulfonate and 30g of deionized water, stirring at normal temperature to obtain an emulsifier aqueous solution, slowly adding 0.1g of N-hydroxymethyl acrylamide, fully mixing, then adding a mixed monomer consisting of 40g of butyl acrylate, 40g of isooctyl acrylate, 2.0g of hydroxyethyl acrylate, 1g of acrylic acid, 1.2g of N-hydroxymethyl acrylamide, 0.2g of ethylene glycol diacrylate, 0.2g of triethylene glycol diacrylate and 10g of methyl methacrylate, stirring for 45min, and stirring at the speed of 600r/min to obtain a pre-emulsion;
2) adding 60g of deionized water and 0.1g of sodium bicarbonate into a reaction kettle, heating to 82 ℃, and injecting 6.86g of pre-emulsion; then 0.438g of ammonium persulfate is dissolved by 10g of deionized water and then added into the reaction kettle, and the reaction is carried out for 20min after a blue phase appears in the system;
3) after the reaction is finished, 0.292g of ammonium persulfate is added into 30g of deionized water to be dissolved, and an initiator solution is prepared; dropwise adding the rest of pre-emulsion and initiator solution at 80 ℃ for 4.0 h;
4) after the dropwise addition, heating the reaction kettle to 88 ℃, reacting for 1 hour, cooling to 40 ℃, adding 1.6g of ammonia water, adjusting the pH value to 7-8, filtering by a 300-mesh sieve, and discharging to obtain the component A.
5) 100g of component A is weighed into a beaker, and stirring is started.
6) 0.5g of the total amount of the components are weighedThe component B (aziridine crosslinking agent SAC-100) was added to 4g of deionized water, stirred with a glass rod until uniform, added to the component A, and stirred for a further 20 min. Coating the prepared pressure-sensitive adhesive on a substrate, and controlling the gluing amount to be 3 +/-1 g/m2And obtaining the protective film.
In the case of the example 3, the following examples are given,
1) weighing 0.2g of ammonium nonylphenol polyoxyethylene ether sulfate, 0.3g of sodium dodecyl diphenyl ether disulfonate and 30g of deionized water, stirring at normal temperature to obtain an emulsifier aqueous solution, then adding a mixed monomer consisting of 50g of butyl acrylate, 20g of isooctyl acrylate, 5g of butyl methacrylate, 8g of methyl methacrylate, 1g of hydroxyethyl acrylate, 1g of acrylic acid, 0.2g of ethylene glycol diacrylate and 0.3g of N-methoxy methacrylamide, stirring for 45min, and stirring at the speed of 600r/min to obtain a pre-emulsion;
2) adding 20g of deionized water into a reaction kettle, heating to 80 ℃, and then injecting 5.80g of pre-emulsion; meanwhile, 0.18g of ammonium persulfate is dissolved by 15g of deionized water and then added into the reaction kettle, and the reaction is carried out for 15min after a blue phase appears in the system;
3) after the reaction is finished, adding 0.12g of ammonium persulfate into 15g of deionized water for full dissolution to prepare an initiator solution; dropwise adding the rest of the pre-emulsion and the initiator solution at 82 ℃ for 3.5 h;
4) after the dropwise addition, heating the reaction kettle to 85 ℃, reacting for 1.5h, cooling to 40 ℃, adding 0.5g of ammonia water, adjusting the pH value to 7-8, filtering by a 300-mesh sieve, and discharging to obtain the component A.
5) 100g of component A is weighed into a beaker, and stirring is started.
6) 0.5g of the component B is weighed, 2g of deionized water is added, the mixture is stirred uniformly by a glass rod and then added into the component A, and the stirring is continued for 20 min. Coating the prepared pressure-sensitive adhesive on a substrate, and controlling the gluing amount to be 3 +/-1 g/m2And the obtained protective film.
In the case of the example 4, the following examples are given,
1) weighing 2g of sodium dodecyl diphenyl ether disulfonate and 30g of deionized water, stirring at normal temperature to obtain an emulsifier aqueous solution, then adding a mixed monomer consisting of 55g of butyl acrylate, 25g of isooctyl acrylate, 8g of butyl methacrylate, 8g of methyl methacrylate, 7g of methyl acrylate, 1g of N-hydroxymethyl acrylamide, 1g of N-methoxy methacrylamide, 1.2g of tripropylene glycol diacrylate, 2g of hydroxypropyl acrylate, 2g of methacrylic acid and 2g of hydroxyethyl acrylate, stirring for 45min, and stirring at the speed of 600r/min to obtain a pre-emulsion;
2) adding 0.2g of sodium bicarbonate and 50g of deionized water into a reaction kettle, heating to 80 ℃, and then injecting 19.42g of pre-emulsion; meanwhile, 0.3g of sodium sulfate and 0.3g of ammonium persulfate are dissolved by 30g of deionized water and then added into the reaction kettle, and the reaction is carried out for 20min after a blue phase appears in the system;
3) after the reaction is finished, adding 30g of deionized water into 0.2g of sodium sulfate and 0.2g of ammonium persulfate to dissolve fully to prepare an initiator solution; dropwise adding the rest of pre-emulsion and initiator solution at 80 ℃ for 4 h;
4) after the dropwise addition, heating the reaction kettle to 86 ℃, reacting for 1.5h, cooling to 40 ℃, adding 2g of ammonia water, adjusting the pH value to 7-8, filtering with a 300-mesh sieve, and discharging to obtain the component A.
5) 100g of component A is weighed into a beaker, and stirring is started.
6) 0.5g of the component B is weighed, 2g of deionized water is added, the mixture is stirred uniformly by a glass rod and then added into the component A, and the stirring is continued for 20 min. Coating the prepared pressure-sensitive adhesive on a substrate, and controlling the gluing amount to be 3 +/-1 g/m2And the obtained protective film.
In the case of the example 5, the following examples were conducted,
1) weighing 1g of sodium dodecyl diphenyl ether disulfonate and 30g of deionized water, stirring at normal temperature to obtain an emulsifier aqueous solution, then adding 50g of butyl acrylate, 20g of isooctyl acrylate, 10g of methyl methacrylate, 0.5g of glycidyl methacrylate, 0.5g N-hydroxymethyl acrylamide, 0.3g of triethylene glycol diacrylate, 0.3g of polyethylene glycol (400) diacrylate, 0.3g of tripropylene glycol diacrylate and 3g of methacrylic acid to form a mixed monomer, stirring for 45min at a stirring speed of 600r/min to obtain a pre-emulsion;
2) adding 0.1g of sodium bicarbonate and 40g of deionized water into a reaction kettle, heating to 80 ℃, and then injecting 8.2g of pre-emulsion; meanwhile, 0.3g of sodium persulfate is dissolved by 15g of deionized water and then added into the reaction kettle, and the reaction is carried out for 15-20min after a blue phase appears in the system;
3) after the reaction is finished, adding 0.2g of ammonium persulfate into 15g of deionized water for full dissolution to prepare an initiator solution; dropwise adding the rest of the pre-emulsion and the initiator solution at 81 ℃ for 3.8 h;
4) after the dropwise addition, heating the reaction kettle to 85 ℃, reacting for 1.5h, cooling to 40 ℃, adding 0.8g of ammonia water, adjusting the pH value to 7-8, filtering by a 300-mesh sieve, and discharging to obtain the component A.
5) 100g of component A is weighed into a beaker, and stirring is started.
6) Weighing 1g of the component B, adding 4g of deionized water, stirring uniformly by using a glass rod, adding the mixture into the component A, and continuing stirring for 20 min. Coating the prepared pressure-sensitive adhesive on a substrate, and controlling the gluing amount to be 3 +/-1 g/m2And the obtained protective film.
In the case of the example 6, it is shown,
1) weighing 0.2g of ammonium nonylphenol polyoxyethylene ether sulfate, 0.3g of sodium dodecyl diphenyl ether disulfonate and 30g of deionized water, stirring at normal temperature to obtain an emulsifier aqueous solution, adding a mixed monomer consisting of 50g of butyl acrylate, 30g of butyl methacrylate, 13g of methyl methacrylate, 0.5g of glycidyl methacrylate, 0.5g of allyl methacrylate, 0.5g of ethylene glycol diacrylate, 1g of hydroxyethyl acrylate and 1g of acrylic acid, stirring for 45min, and stirring at the speed of 600r/min to obtain a pre-emulsion;
2) adding 30g of deionized water into a reaction kettle, heating to 80 ℃, and then injecting 7.62g of pre-emulsion; meanwhile, 0.48g of ammonium persulfate is dissolved by 20g of deionized water and then added into the reaction kettle, and the reaction is carried out for 18min after a blue phase appears in the system;
3) after the reaction is finished, adding 20g of deionized water into 0.32g of ammonium persulfate to dissolve fully to prepare an initiator solution; dropwise adding the rest of pre-emulsion and initiator solution at 81 ℃ for 3.7 h;
4) after the dropwise addition, heating the reaction kettle to 86 ℃, reacting for 1.5h, cooling to 40 ℃, adding 1.2g of ammonia water, adjusting the pH value to 7-8, filtering by a 300-mesh sieve, and discharging to obtain the component A.
5) 100g of component A is weighed into a beaker, and stirring is started.
6) Weighing 2g of the component B, adding 8g of deionized water, stirring uniformly by using a glass rod, adding into the component A, and continuing stirring for 20 min. Coating the prepared pressure-sensitive adhesive on a substrate, and controlling the gluing amount to be 3 +/-1 g/m2And the obtained protective film.
In the comparative example 1,
1) weighing 1.2g of ammonium nonylphenol polyoxyethylene ether sulfate and 30g of deionized water, stirring at normal temperature to obtain an emulsifier aqueous solution, adding a mixed monomer consisting of 70g of butyl acrylate, 5g of isooctyl acrylate, 1.2g of hydroxypropyl acrylate, 0.7g of acrylic acid and 15g of methyl methacrylate, stirring for 45min at the stirring speed of 600r/min to obtain a pre-emulsion;
2) adding 40g of deionized water and 0.1g of sodium bicarbonate into a reaction kettle, heating to 80 ℃, and then injecting 9.23g of pre-emulsion; then dissolving 0.36g of sodium persulfate by 10g of deionized water, adding the sodium persulfate into the reaction kettle when the temperature of the reaction kettle is stabilized at 80 ℃, and reacting for 15min when a blue phase appears in the system;
3) adding 0.24g of sodium persulfate into 30g of deionized water for dissolution to prepare an initiator solution; after the initial reaction is finished, the residual pre-emulsion and the initiator solution are dripped at 80 ℃ for 3.5 hours;
4) after the dropwise addition, heating the reaction kettle to 85 ℃, reacting for 1.5 hours, cooling to 40 ℃, adding 1.5g of ammonia water and 10g of deionized water, adjusting the pH value to 7-8, filtering by a 300-mesh sieve, and discharging to obtain the component A.
5) 100g of component A is weighed into a beaker, and stirring is started.
6) 0.5g of the component B (aziridine crosslinking agent SAC-100) is weighed, 4g of deionized water is added, the mixture is stirred uniformly by a glass rod and then added into the component A, and the stirring is continued for 20 min. Coating the prepared pressure-sensitive adhesive on a substrate, and controlling the gluing amount to be 3 +/-1 g/m2And finally obtaining the protective film.
The protective films prepared in examples 1 to 6 and comparative example 1 were subjected to the following performance test:
1. uniformly coating the mixture on a 25-micron PET film by using a coater, drying the mixture for 3-5 min at the temperature of 85 +/-2 ℃, taking out the dried mixture, and observing the crystal point condition of the glue surface;
2. 180 ° peel strength test: the test method is determined according to the test method of 180 DEG peeling strength of the pressure-sensitive adhesive tape GB 2792-1998.
3. And (3) testing initial adhesion: the test was carried out according to the inclined plane rolling ball method of GB 4852-1984.
4. And (3) testing the resistance to wet heat and aging: and (3) attaching the protective film on the mother glass, taking out the mother glass after being placed in an environment of 60 ℃/90% RH for 3 days, tearing the protective film, and observing the conditions of adhesive residues and mottled shadows.
The data are as follows in table 1:
as can be seen from the comparison of the performance test data of comparative example 1 and example 1 in Table 1, when acrylate with two double bonds is used as a functional monomer, the basic performance of the adhesive is not greatly affected after the acrylate is added, the gel fraction of the system is low, and the adhesive has good wetting compatibility, when the water-based acrylate pressure-sensitive adhesive prepared by the functional monomer is coated on a substrate to form a protective film, the adhesive surface has no obvious crystal points, the transparency is good, the attaching effect of the smooth surface is good, no adhesive residue and no mottle are generated in the protective film removing process, and the water-based acrylate pressure-sensitive adhesive also has good humidity resistance and heat resistance and aging resistance.
As can be seen from the performance test data of the embodiments 1 to 6 in Table 1, when the aqueous acrylate pressure-sensitive adhesive of the present invention is subjected to emulsion copolymerization with the acrylate monomers of two double bonds in the component A, only one double bond participates in the polymerization reaction at the initial stage due to the influence of steric hindrance, so as to generate an acrylate polymer with only slight crosslinking, and in the later-stage film forming process, the acrylate polymer is further deeply crosslinked with an additional crosslinking agent under a higher condition to improve the cohesive force, thereby realizing moisture and heat resistance without residual adhesive ghost.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The water-based acrylate pressure-sensitive adhesive is characterized by comprising a component A and a component B, wherein the component A comprises the following raw material components in parts by mass: 75 to 88 mass portions of soft monomer, 8 to 15 mass portions of hard monomer, 2 to 6 mass portions of polar monomer, 0.3 to 2 mass portions of internal crosslinking monomer, 0.5 to 2 mass portions of anionic emulsifier, 0.2 to 1.2 mass portions of functional monomer, 0 to 0.2 mass portion of buffering agent, 0.3 to 1 mass portion of initiator, 80 to 140 mass portions of deionized water and 0.5 to 2 mass portions of pH value regulator,
wherein component B comprises a trifunctional aziridine-based crosslinking agent.
2. The aqueous acrylate pressure sensitive adhesive of claim 1 wherein the soft monomer comprises one or more of butyl acrylate, butyl methacrylate, and isooctyl acrylate.
3. The aqueous acrylate pressure-sensitive adhesive of claim 1 wherein the hard monomer comprises one or both of methyl acrylate and methyl methacrylate.
4. The aqueous acrylate pressure sensitive adhesive of claim 1 wherein the polar monomer comprises one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate and hydroxypropyl acrylate.
5. The aqueous acrylate pressure-sensitive adhesive of claim 1 wherein the internal crosslinking monomer comprises one or more of glycidyl methacrylate, N-methylolacrylamide and N-methoxy methacrylamide.
6. The aqueous acrylate pressure-sensitive adhesive of claim 1 wherein the anionic emulsifier comprises one or both of ammonium nonylphenol polyoxyethylene ether sulfate and sodium dodecyl diphenyl ether disulfonate.
7. The aqueous acrylate pressure-sensitive adhesive of claim 1 wherein the functional monomer is an acrylate containing two double bonds including one or more of allyl methacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol (400) diacrylate, tripropylene glycol diacrylate.
8. The aqueous acrylate pressure-sensitive adhesive of claim 1 wherein the buffering agent comprises sodium bicarbonate; the pH value regulator comprises ammonia water.
9. The aqueous acrylate pressure-sensitive adhesive of claim 1 wherein the initiator comprises one or both of sodium persulfate and ammonium persulfate.
10. Use of any one of the aqueous acrylate pressure-sensitive adhesives of claims 1-9 in a protective film.
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CN105219311A (en) * | 2014-06-10 | 2016-01-06 | 湖北航天化学技术研究所 | A kind of preparation of water soluble acrylic acid ester pressure-sensitive and application thereof |
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CN115287014B (en) * | 2022-07-07 | 2024-01-26 | 江苏景宏新材料科技有限公司 | Water-based acrylate pressure-sensitive adhesive for protective film and preparation method thereof |
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