CN116948571A - Acrylic pressure-sensitive adhesive and preparation method thereof - Google Patents
Acrylic pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN116948571A CN116948571A CN202310942747.8A CN202310942747A CN116948571A CN 116948571 A CN116948571 A CN 116948571A CN 202310942747 A CN202310942747 A CN 202310942747A CN 116948571 A CN116948571 A CN 116948571A
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- acrylate
- sensitive adhesive
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 118
- 239000002904 solvent Substances 0.000 claims abstract description 65
- 239000003999 initiator Substances 0.000 claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 35
- -1 acrylic ester Chemical class 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 117
- 239000011259 mixed solution Substances 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 10
- 239000002390 adhesive tape Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010998 test method Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000003522 acrylic cement Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses an acrylic pressure-sensitive adhesive and a preparation method thereof, wherein the acrylic pressure-sensitive adhesive is prepared from the following raw materials: acrylate monomer, solvent and initiator; the acrylic ester monomer comprises soft monomer accounting for 75-95% of the total mass of the acrylic ester monomer and functional monomer accounting for 5-12% of the total mass of the acrylic ester monomer; functional monomers include glycidyl acrylate and methacrylate. The acrylic pressure-sensitive adhesive has high temperature and high humidity resistance, the 180 DEG stripping force can be between 6 and 16N/25mm, the holding force can be more than 72 hours under the condition of 85 ℃ and 85 percent humidity, the 1kg weight is not dropped or displaced, and the adhesive tape is not degummed after the test is finished.
Description
Technical Field
The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to an acrylic pressure-sensitive adhesive and a preparation method thereof.
Background
The pressure-sensitive adhesive is a high molecular viscoelastic body with both liquid viscosity property and solid elasticity property, objects can be immediately bonded by finger touch pressure, and the pressure-sensitive adhesive is coated on various substrates to obtain pressure-sensitive adhesive products with various properties. The pressure-sensitive adhesive is mainly divided into acrylate pressure-sensitive adhesive, polyurethane pressure-sensitive adhesive, organic silicon pressure-sensitive adhesive, thermoplastic elastomer pressure-sensitive adhesive, other pressure-sensitive adhesives and the like according to the types of main adhesives, and the acrylate pressure-sensitive adhesive has excellent adhesive property and good interfacial stress dispersing capability on various base materials, has the characteristics of relatively low price, excellent weather resistance, heat resistance, no phase separation and migration phenomenon and the like, has good transparency, has no influence on skin, and is the pressure-sensitive adhesive with the widest application range at present.
At present, the automation and the intellectualization of the production in the electronic and electric industry are gradually replaced by pressure sensitive adhesive in the traditional structural bonding mode, and the conventional pressure sensitive adhesive tape is difficult to meet the high-temperature and high-humidity requirements of the use environment of bonded products due to the characteristics of the main adhesive.
The patent CN115960302B discloses an acrylic adhesive, which adopts raw materials including butyl acrylate, isooctyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate, tert-butyl acrylate, glycidyl methacrylate, beta-carboxyethyl acrylate, ethyl acetate and the like, and the prepared pressure-sensitive adhesive product has excellent adhesive property and high-temperature high-humidity rebound resistance through the collocation of tackifying resins with high softening point and medium-low softening point, and has higher crosslinking degree and good water vapor resistance through the synergistic cooperation of an epoxy curing agent and an isocyanate curing agent.
Disclosure of Invention
The invention provides an acrylic pressure-sensitive adhesive and a preparation method thereof, which can solve the problems of multiple raw material components, high production cost and complex process of the high-temperature and high-humidity-resistant pressure-sensitive adhesive in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in one aspect of the invention, an acrylic pressure-sensitive adhesive is provided, which is prepared from the following raw materials: acrylate monomer, solvent and initiator;
the acrylic ester monomer comprises soft monomer accounting for 75-95% of the total mass of the acrylic ester monomer and functional monomer accounting for 5-12% of the total mass of the acrylic ester monomer;
the functional monomers include glycidyl acrylate and methacrylate.
Alternatively, the mass fraction of soft monomer is independently selected from 75%, 80%, 85%, 90%, 95% of the total mass of acrylate monomer.
Alternatively, the mass fraction of functional monomer is independently selected from 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12% of the total mass of acrylate monomers.
In the invention, the soft monomer and the functional monomer comprise acrylic acid and glycidyl methacrylate, and the soft monomer provides soft film forming property, extensibility and adhesive force for the pressure-sensitive adhesive; the addition of the acrylic acid and the glycidyl methacrylate containing the acryl functional groups can reduce the glass transition temperature of the acrylic acid pressure-sensitive adhesive, increase the flexibility of the adhesive, enable the adhesive to better adapt to the deformation and expansion of materials in a high-temperature and high-humidity environment, enable the contact area of the adhesive and a substrate to be increased by the existence of the acrylic acid and the glycidyl methacrylate, enhance the adhesion force, improve the bonding performance in the high-temperature and high-humidity environment, enable the acrylic acid and the glycidyl methacrylate to have better heat resistance, and keep stable performance in the high-temperature environment, so that the bonding performance of the acrylic acid pressure-sensitive adhesive in the high-temperature and high-humidity environment is improved.
In addition, the functional monomer glycidyl methacrylate can be properly crosslinked in the reaction process, and a part of residual epoxy groups still remain in the final product, so that the epoxy groups are opened in a high-temperature and high-humidity environment, and the generated hydroxyl is more firmly bonded with the bonded surface, thereby realizing the stable performance of the product in the high-temperature and high-humidity environment.
As still further aspects of the invention: the acrylic acid accounts for 4-10% of the total mass of the acrylic ester monomer, and the glycidyl methacrylate accounts for 0.5-2% of the total mass of the acrylic ester monomer;
and/or the functional monomer further comprises at least one of hydroxybutyl acrylate, hydroxypropyl acrylate or hydroxyethyl acrylate.
Alternatively, the mass fraction of acrylic acid is independently selected from 4%, 5%, 6%, 7%, 8%, 9%, 10% of the total mass of acrylate monomers.
Alternatively, the mass fraction of glycidyl methacrylate is independently selected from 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2% of the total mass of acrylate monomers.
As still further aspects of the invention: the acrylate monomer also comprises a hard monomer accounting for 0-13% of the total mass of the acrylate monomer;
further preferably, the content of the hard monomer is 8-13% of the total mass of the acrylate monomer;
and/or the hard monomer is at least one selected from methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran methacrylate, vinyl acetate, cyclohexyl methacrylate and benzyl methacrylate.
Alternatively, the mass fraction of hard monomer is independently selected from 0%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% of the total mass of acrylate monomer.
As still further aspects of the invention: the soft monomer is at least one selected from butyl acrylate, methyl acrylate, ethyl acrylate and isooctyl acrylate;
further preferably, the soft monomer is butyl acrylate.
As still further aspects of the invention: the solvent is at least one selected from toluene, ethyl acetate, butyl acetate, sec-butyl acetate, cyclohexane, n-hexane, acetone, methanol and methyl acetate, and the azeotropic point of the solvent is below 65 ℃;
and/or the initiator is selected from azodiisobutyronitrile or azodiisoheptonitrile, and the initiator is 0.1-1% of the total mass of the acrylate monomer.
Alternatively, the mass fraction of initiator is independently selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% of the total mass of acrylate monomers.
As still further aspects of the invention: the solid content of the acrylic pressure-sensitive adhesive is 35-55%.
In another aspect of the present invention, there is provided a method for preparing an acrylic pressure-sensitive adhesive comprising at least:
(1) Uniformly mixing an acrylic ester monomer, a first solvent and a first initiator according to a formula to prepare a mixed solution;
(2) Weighing 25% -45% of the total mass of the mixed solution, stirring, and then dropwise adding the rest mixed solution for 2.5-5 h;
(3) After continuing the reaction for 1-3 hours, adding a second initiator and a second solvent into the reaction kettle at a constant speed for continuing the reaction for 1-2 hours;
(4) And after the heat preservation reaction is finished, adding a third solvent into the reaction system, stirring, and cooling and discharging after the reaction is finished.
The inventor of the present invention found that in the step (2), 25 to 45% of the total mass of the mixed solution is weighed and poured into a reaction kettle, and the initial reaction concentration is controlled, and the preliminary polymerization reaction is carried out so as to control the emulsion particles formed by the polymerization to have a proper molecular weight. Preferably, 25-30% of the total mass of the mixture is poured into the reaction vessel, for example, in one embodiment, about 28% of the total mass of the mixture is poured into the reaction vessel.
As still further aspects of the invention: the first solvent is 70-90%, preferably 80% of the total mass of the acrylate monomers;
and/or, the first initiator is 0.05-0.5% of the total mass of the acrylate monomer;
and/or, the second initiator is 0.05-0.5% of the total mass of the acrylate monomer;
and/or, the second solvent is 15-25% of the total mass of the acrylate monomer;
and/or, the third solvent is 45-55% of the total mass of the acrylate monomer.
The inventor of the present invention found that the performance of the prepared acrylate adhesive is best when the first solvent in the step (1) is 70-90% of the total mass of the acrylate monomers, i.e. the mass concentration of the acrylate monomers in the mixed solution is controlled to be 50-60%, and more preferably about 55%. If the concentration of the acrylic ester monomer in the mixed solution is too high, the heat generated by the reaction is difficult to release, and polymerization failure can be caused; if the concentration of the acrylate monomer in the mixed solution is too low, the molecular weight of the product is too low due to chain transfer of the solvent, and the desired properties of the product are not achieved.
In the invention, the first solvent, the second solvent and the third solvent are all independently selected from at least one of toluene, ethyl acetate, butyl acetate, sec-butyl acetate, cyclohexane, n-hexane, acetone, methanol and methyl acetate. The first solvent, the second solvent and the third solvent may be the same or different.
The first initiator and the second initiator are independently selected from azodiisobutyronitrile or azodiisoheptonitrile, and the first initiator and the second initiator can be the same or different.
As still further aspects of the invention: in the step (2), the temperature in the reaction kettle is controlled to be 65-80 ℃.
And/or the stirring rate is 50-150rpm/min.
As still further aspects of the invention: in the step (4), the stirring time is 1-2h.
The invention has the beneficial effects that:
(1) According to the invention, when the technical problem that the adhesive performance (especially the adhesive holding force) of the acrylic pressure-sensitive adhesive is poor in a high-temperature and high-humidity environment is solved, the acrylic acid ester monomer and the functional monomer are mixed, the functional monomers of acrylic acid and glycidyl methacrylate are introduced on the basis of taking a soft monomer as a main monomer, and the adhesive performance of the pressure-sensitive adhesive in the high-temperature and high-humidity environment is improved by controlling the preparation process and polymerizing a plurality of simple monomer raw materials under the condition that a curing agent and a tackifying resin are not introduced.
(2) The 180-degree peel force test of the high-temperature and high-humidity resistant acrylic pressure-sensitive adhesive can be between 6 and 16N/25mm, the holding force can be more than 72 hours under the condition of 85 ℃ and 85 percent of humidity, the 1kg weight is free from dropping and displacement, and the adhesive tape is not degummed after the test is finished.
Detailed Description
The following detailed description of the present invention is provided in connection with embodiments, and the technical solutions of the present invention are clearly and completely described so as to facilitate understanding of the present invention by those skilled in the art, and the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Meanwhile, the raw materials mentioned below are not specified, and are all commercial products; the process steps or preparation methods not mentioned in detail are those known to the person skilled in the art.
The performance test method in the invention comprises the following steps:
1. 180℃peel strength test method for pressure-sensitive adhesive tapes was determined according to method 1 in GB/T2792-2014 test method for peel strength of adhesive tapes.
2. The high-temperature high-humidity performance test method comprises the steps of sticking the prepared adhesive tape onto a clean steel plate, measuring the adhesive tape and the steel plate by referring to a method G in the standard of adhesive tape adhesion test method GB/T4851-2014, and putting the steel plate hung with weights into a constant-temperature constant-humidity box, wherein the temperature of the constant-temperature constant-humidity box is set to be 85 ℃, and the relative humidity is set to be 85%.
3. The initial tackiness test method was determined according to the inclined plane ball method A in GB/T4852-2002 "pressure sensitive adhesive tape initial tackiness test method (ball method)" standard.
4. The solid content test is carried out with reference to GB/T2793-1995 determination of adhesive non-volatile content.
Example 1
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 70 ℃ and the stirring speed to be 100rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 1
Example 2
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 75 ℃, and controlling the stirring speed to be 150rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 2
Example 3
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 45 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 65 ℃ and the stirring speed to be 100rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 3 Table 3
Example 4
(1) Firstly, uniformly mixing a soft monomer, a functional monomer, a first solvent and a first initiator, then weighing 51 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 72 ℃, and stirring at a speed of 100rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 4 Table 4
Example 5
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 76 ℃ and the stirring speed to be 100rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 5
Example 6
(1) Firstly, uniformly mixing a soft monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 80 ℃ and the stirring speed to be 50rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 6
Example 7
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 68 ℃ and the stirring speed to be 50rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 7
Example 8
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 73 ℃ and the stirring speed to be 50rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 8
Example 9
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 78 ℃ and the stirring speed to be 50rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 9
Comparative example 1
In contrast to example 1, the functional monomer acrylic acid was not added and replaced by the soft monomer butyl acrylate.
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 65-80 ℃ and the stirring speed to be 100rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
Table 10
Comparative example 2
In contrast to example 1, the functional monomer glycidyl methacrylate was not added and replaced by the soft monomer butyl acrylate.
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then weighing 50 parts of mixed solution, pouring the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 65-80 ℃ and the stirring speed to be 100rpm/min;
(2) After the polymerization reaction starts, the rest mixed solution is dripped for 3 hours, after the dripping is finished, the reaction is continued for 2 hours, a second initiator and a second solvent are added into the reaction kettle in a dripping mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
TABLE 11
Comparative example 3
In contrast to example 1, the preparation process is different, and the mixed solution in step (1) is poured into the reaction kettle all at once. The components and amounts of the raw materials for the acrylic adhesive were the same as in example 1.
(1) Firstly, uniformly mixing a soft monomer, a hard monomer, a functional monomer, a first solvent and a first initiator, then pouring all the mixed solution into a reaction kettle, controlling the temperature in the reaction kettle to be 65-80 ℃, and performing polymerization reaction at the stirring speed of 100rpm/min;
(2) After the polymerization reaction is carried out for 3 hours, a second initiator and a second solvent are added into a reaction kettle in a dropwise adding mode, and the reaction is continued for 2 hours;
(3) After the heat preservation reaction is finished, adding a third solvent into the reaction system, continuously stirring for 2 hours, cooling and discharging after the reaction is finished, and controlling the solid content to be between 35 and 55 percent.
Comparative example 4
The first solvent was used in an amount of 60 parts by weight of toluene and 45 parts by weight of n-hexane, which was different from that of example 1, and the other components were the same as those of example 1.
Comparative example 5
The first solvent was used in an amount of 35 parts by weight of toluene and 25 parts by weight of n-hexane, which was different from that of example 1, and the other components were the same as those of example 1. In the experimental reaction process, demulsification and slag discharge conditions appear, and polymerization fails.
The glue solutions prepared in examples 1 to 9 and comparative examples 1 to 4 were partially coated on a 25.+ -.2 μm PET film using a coater, the thickness was controlled to 25.+ -.2. Mu.m, the glue solution was cured at 110℃for 3 minutes, and then the test pieces were further cured in a 50℃oven for 48 hours, and the test results are shown in Table 12. Wherein, the adhesion test condition is that the temperature is 85 ℃ and the relative humidity is 85%; the residual glue condition is the phenomenon of the surface of the steel plate after the holding and sticking test.
Table 12
As can be seen from the table, the high-temperature and high-humidity resistant acrylic pressure-sensitive adhesive is a mixture of solution polymerized acrylic resin, the solid content of the pressure-sensitive adhesive is 35-55%, the 180-DEG peeling force test can be between 6 and 16N/25mm, the holding force can be 72 hours under the condition of 85 ℃ and 85% humidity, a 1kg weight is free from dropping and displacement, and the adhesive tape is torn off and is not degummed after the test is completed.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It is specifically intended that the embodiments be described and further illustrated only for the preferred additive formulation content of the present invention and not as limitations on the scope of the invention, as various modifications to these embodiments will be apparent to those skilled in the art, and thus, in light of the above teachings, insubstantial improvements and adaptations of the invention that are intended to be within the scope of the invention and are not intended to be limited to the embodiments shown herein but are to be accorded the broadest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The acrylic pressure-sensitive adhesive is characterized by being prepared from the following raw materials: acrylate monomer, solvent and initiator;
the acrylic ester monomer comprises soft monomer accounting for 75-95% of the total mass of the acrylic ester monomer and functional monomer accounting for 5-12% of the total mass of the acrylic ester monomer;
the functional monomers include glycidyl acrylate and methacrylate.
2. The acrylic pressure-sensitive adhesive according to claim 1, wherein the acrylic acid is 4 to 10% of the total mass of the acrylate monomers, and the glycidyl methacrylate is 0.5 to 2% of the total mass of the acrylate monomers;
and/or the functional monomer further comprises at least one of hydroxybutyl acrylate, hydroxypropyl acrylate or hydroxyethyl acrylate.
3. The acrylic pressure-sensitive adhesive according to claim 1, wherein the acrylate monomer further comprises a hard monomer accounting for 0 to 13% of the total mass of the acrylate monomer;
further preferably, the content of the hard monomer is 8-13% of the total mass of the acrylate monomer;
and/or the hard monomer is at least one selected from methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, tetrahydrofuran methacrylate, vinyl acetate, cyclohexyl methacrylate and benzyl methacrylate.
4. The acrylic pressure-sensitive adhesive according to claim 1, wherein the soft monomer is at least one selected from butyl acrylate, methyl acrylate, ethyl acrylate, isooctyl acrylate;
further preferably, the soft monomer is butyl acrylate.
5. The acrylic pressure-sensitive adhesive according to claim 1, wherein the solvent is at least one selected from toluene, ethyl acetate, butyl acetate, sec-butyl acetate, cyclohexane, n-hexane, acetone, methanol, methyl acetate, and the solvent has an azeotropic point of 65 ℃ or lower;
and/or the initiator is selected from azodiisobutyronitrile or azodiisoheptonitrile, and the initiator is 0.1-1% of the total mass of the acrylate monomer.
6. The acrylic pressure-sensitive adhesive according to claim 1, wherein the acrylic pressure-sensitive adhesive has a solids content of 35 to 55%.
7. The method for producing an acrylic pressure-sensitive adhesive according to any one of claims 1 to 6, comprising the steps of:
(1) Uniformly mixing an acrylic ester monomer, a first solvent and a first initiator according to a formula to prepare a mixed solution;
(2) Weighing 25% -45% of the total mass of the mixed solution, stirring, and then dropwise adding the rest mixed solution for 2.5-5 h;
(3) After continuing the reaction for 1-3 hours, adding a second initiator and a second solvent into the reaction kettle at a constant speed for continuing the reaction for 1-2 hours;
(4) And after the heat preservation reaction is finished, adding a third solvent into the reaction system, stirring, and cooling and discharging after the reaction is finished.
8. The method for producing an acrylic pressure-sensitive adhesive according to claim 7, wherein the first solvent is 70 to 90%, preferably 80% of the total mass of the acrylate monomer;
and/or, the first initiator is 0.05-0.5% of the total mass of the acrylate monomer;
and/or, the second initiator is 0.05-0.5% of the total mass of the acrylate monomer;
and/or, the second solvent is 15-25% of the total mass of the acrylate monomer;
and/or, the third solvent is 45-55% of the total mass of the acrylate monomer.
9. The method for producing an acrylic pressure-sensitive adhesive according to claim 7, wherein in the step (2), the temperature in the reaction vessel is controlled to be 65 to 80 ℃;
and/or the stirring rate is 50-150rpm/min.
10. The method for producing an acrylic pressure-sensitive adhesive according to claim 7, wherein in the step (4), the stirring time is 1 to 2 hours.
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