CN103756602B - A kind of protective membrane acrylate pressure-sensitive adhesive and preparation method thereof - Google Patents
A kind of protective membrane acrylate pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN103756602B CN103756602B CN201410013570.4A CN201410013570A CN103756602B CN 103756602 B CN103756602 B CN 103756602B CN 201410013570 A CN201410013570 A CN 201410013570A CN 103756602 B CN103756602 B CN 103756602B
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 49
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 41
- 230000001681 protective effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000012528 membrane Substances 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 78
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000003999 initiator Substances 0.000 claims description 41
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000004014 plasticizer Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 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 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 229920003052 natural elastomer Polymers 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- -1 polyoxypropylene diisocyanate Polymers 0.000 description 5
- 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 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 206010010071 Coma Diseases 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 241001112258 Moca Species 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention discloses a kind of protective membrane acrylate pressure-sensitive adhesive and preparation method thereof, mix primarily of the following raw material with parts by weight: polymer A? 100 parts; Polymer B? 5-50 part; Compound C? 0.2-2 part; Polymer A is the polymkeric substance containing crosslinkable functionality, and its second-order transition temperature is between-10 DEG C to-65 DEG C; Polymer B is not containing the polymkeric substance of crosslinkable functionality, and it is formed lower than the monomer copolymerization of zero degree or homopolymerization by second-order transition temperature, or formed by hard monomer and soft monomer copolymerization; Compound C is the compound of amino-contained, polyvalent metal compounds or the compound containing isocyanate group.The present invention uses vinyl acetic monomer to synthesize the acrylate pressure-sensitive adhesive with rubber pressure-sensitive adhesive performance, there is good initial bonding strength, peeling force and hold tack, energy consumption need not be plastified low in the course of processing, aromatic hydrocarbon solvent does not dissolve, reduce the harm of people and avoid catching fire, to be heated and not easily aging under illumination.
Description
Technical Field
The invention relates to a pressure-sensitive adhesive, in particular to an acrylate pressure-sensitive adhesive for a protective film and a preparation method thereof.
Background
The pressure-sensitive adhesive is an adhesive closely related to daily life of people, and is one of the most widely applied adhesives with the largest output at present. The pressure-sensitive adhesive is distinguished from the main chemical components of the pressure-sensitive adhesive, and can be divided into rubber pressure-sensitive adhesive, thermoplastic elastic pressure-sensitive adhesive, polyacrylate pressure-sensitive adhesive, polyvinyl ether pressure-sensitive adhesive, organic silicon pressure-sensitive adhesive and the like. At present, rubber-type pressure-sensitive adhesives are prepared from natural rubber or synthetic rubber in combination with appropriate tackifying resins, softeners and the like. The rubber is a main component, which endows the pressure-sensitive adhesive with enough cohesive strength, good tensile strength and elongation; the tackifying resin enables the pressure-sensitive adhesive to have certain adhesiveness, and the softening agent is used for reducing the bulk viscosity of the pressure-sensitive adhesive and improving the initial adhesion at low temperature. The process is to plasticate and dissolve natural rubber, and then to add tackifying resin and plasticizer. The process has the following difficulties: 1. in the plastication process, the plasticizing degree of the natural rubber is difficult to control, and the energy consumption is high; 2. aromatic hydrocarbon solvents such as toluene are used for dissolving the rubber. As is well known, aromatic hydrocarbon solvents are harmful to human bodies, stimulate central nerves of brains and narcotize coma, and although some processes adopt a method of reducing the using amount of aromatic hydrocarbon to reduce the harm to the human bodies, new danger is brought because solvent gasoline is used, and fire disasters are easy to happen; 3. because unsaturated bonds exist on the molecular chain of the natural rubber, the natural rubber is easy to age under heating and illumination, so that the natural rubber cannot be used. Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the acrylate pressure-sensitive adhesive for the protective film, which is synthesized by using ethyl acetate, has the performance similar to that of a rubber type pressure-sensitive adhesive, namely has good initial adhesion, stripping force and permanent adhesion, does not need to be plasticized in the processing process, has low energy consumption, does not need aromatic hydrocarbon solvents to be dissolved, reduces the harm to people and avoids the danger of fire, and is not easy to age under heat and light.
The invention also aims to provide a preparation method of the acrylate pressure-sensitive adhesive for the protective film.
The technical scheme adopted by the invention for realizing the aim is as follows:
the acrylate pressure-sensitive adhesive for the protective film is characterized by being mainly prepared from the following raw materials in parts by weight:
100 parts of a polymer A;
5-50 parts of polymer B;
0.2-2 parts of a compound C;
wherein,
the polymer A is a polymer containing crosslinkable functional groups, and the glass transition temperature of the polymer A is between-10 ℃ and-65 ℃;
the polymer B is a polymer without crosslinkable functional groups, and is formed by copolymerization or homopolymerization of monomers with the glass transition temperature lower than zero, or copolymerization of hard monomers and soft monomers;
the compound C is an amino group-containing compound, a polyvalent metal compound or an isocyanate group-containing compound.
The high or low glass transition temperature is an important index reflecting the softness and brittleness of the polymer. The higher homopolymer glass transition temperature of the monomer is called a hard monomer, which increases the hardness and tensile strength of the copolymer resin. As the hard monomer, there are usually used methyl acrylate (8 ℃ C.), vinyl acetate (22 ℃ C.), styrene (80 ℃ C.), acrylonitrile (97 ℃ C.), methyl methacrylate (105 ℃ C.), acrylamide (165 ℃ C.), etc. Monomers having a glass transition temperature of-20 ℃ to-70 ℃ are generally called soft monomers, and commonly used soft monomers include ethyl acrylate (-22 ℃), butyl acrylate (-55 ℃), isooctyl acrylate (-70 ℃) and the like.
As a preferred embodiment of the present invention, the polymer A comprises the following raw materials, by weight, 0-30 parts of ethylenically unsaturated acid, 80-95 parts of acrylate, and 0.5-10 parts of monomer containing crosslinkable functional group; the polymer B comprises the following raw materials, by weight, 60-100 parts of acrylate and 0-20 parts of methacrylate monomer;
as a preferable scheme of the invention, the polymer A is prepared from the following raw materials in parts by weight: 80-95 parts of acrylate monomer, 5-20 parts of methacrylate monomer or acrylic acid; 0.5-10 parts of acrylate monomers; 0.2-1 part of initiator; 100 portions of ethyl acetate and 150 portions of polymer B, wherein the polymer B is prepared from the following raw materials in parts by weight: 60-100 parts of acrylate monomer; 1-15 parts of a methacrylate monomer; 0.2-1 part of initiator; 100 portions of ethyl acetate and 150 portions of ethyl acetate.
In a preferred embodiment of the present invention, the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, and isooctyl acrylate.
In a preferred embodiment of the present invention, the methacrylate monomer is one or more of methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
In a preferred embodiment of the present invention, the hydroxy acrylate monomer is acrylamide and its derivatives, and the acrylamide derivative is preferably one or more selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxymethyl acrylamide.
As a preferred embodiment of the present invention, the initiator is azobisisobutyronitrile;
as a preferable scheme of the invention, the acrylate pressure-sensitive adhesive for the protective film further comprises tackifying resin and plasticizer, wherein the dosage of the tackifying resin is 1-30 parts by weight, and the dosage of the plasticizer is 1-10 parts by weight;
in a preferred embodiment of the present invention, the tackifier resin is one of rosin, C5, C9 petroleum resin, and terpene. Among them, rosin is the best, followed by C5 petroleum resin, and terpene has the worst performance.
In a preferred embodiment of the present invention, the plasticizer is dibutyl phthalate, dioctyl phthalate, mineral oil, or the like.
As a preferable embodiment of the present invention, an amine group-containing compound such as polyamine, polyamine coupling agent, etc.; examples are as follows: 3, 3-dichloro-4, 4-diphenylmethanediamine (MOCA), propyleneglycolbis- (4, 4' -diamino) benzoate, polyoxypropylenediamine, triethylenetetramine, etc.
The polyvalent metal compound is butyl titanate, a condensate thereof, or the like, and is exemplified by: butyl titanate, a condensate of butyl titanate and acetylacetone, calcium acetate, aluminum acetylacetonate, and the like.
The isocyanate-containing substance is a substance containing two or more isocyanate groups as a terminal, and is exemplified by the following: polyoxypropylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, and the like.
The invention also aims to provide a preparation method of the acrylate pressure-sensitive adhesive for the protective film, which comprises the following specific steps:
the method is characterized by comprising the following steps:
1) synthesis of Polymer A: adding ethyl acetate into a reaction kettle, starting stirring, adding 20 parts of mixed monomer consisting of acrylate monomer and methacrylate monomer or acrylic acid and acrylic hydroxy ester monomer, and simultaneously adding 0.1 part of initiator; heating to 78 deg.C, maintaining for 0.5-1 hr, and adding the rest monomer containing 0.2-0.4 weight parts of initiator for 3-3.5 hr; after the addition, the temperature is kept for 60 minutes, and the initiator is replenished every three ten minutes; keeping the temperature for 1.5 hours after the initiator is added, cooling and discharging;
2) synthesis of Polymer B: adding ethyl acetate into a reaction kettle, starting stirring, adding 20 parts of mixed monomer consisting of acrylate monomer and methacrylate monomer, and simultaneously adding 0.1 part of initiator; heating to 78 deg.C, maintaining for 0.5-1 hr, and adding the rest monomer containing 0.2-0.4 weight parts of initiator for 3-3.5 hr; after the addition, the temperature is kept for 60 minutes, and the initiator is replenished every three ten minutes; keeping the temperature for 1.5 hours after the initiator is added, cooling and discharging;
3) and (2) mixing the polymer A prepared in the step 1) and the polymer B and the compound C prepared in the step 2) according to the proportion of the first object of the invention, and uniformly mixing to obtain the acrylate pressure-sensitive adhesive for the protective film.
In a preferred embodiment of the present invention, in step 3, the acrylate pressure-sensitive adhesive for a protective film further comprises a tackifying resin and a plasticizer, wherein the amount of the tackifying resin is 1 to 30 parts by weight, and the amount of the plasticizer is 1 to 10 parts by weight.
The invention has the beneficial effects that:
1. the invention uses non-crosslinkable polymer, so the plasticizer is used a little, thus reducing the exudation of small molecules; the two polymers are blended together, one polymer is crosslinked into a network structure, the other polymer still exists in a thermoplastic state in a cured species and does not participate in crosslinking polymerization, so that a novel semi-interpenetrating network polymer is formed, the cured substance has toughness and rigidity, and the formed pressure-sensitive adhesive is ensured to have good initial adhesion, stripping force and permanent adhesion, and the three keep good balance. Meanwhile, plasticization is not needed in the processing process, the energy consumption is low, an aromatic solvent is not needed for dissolution, the harm to people is reduced, the fire danger is avoided, and the aging is not easy to occur under the heating and illumination.
2. The acrylate pressure-sensitive adhesive for the protective film can be coated on various base materials including PP, PE, OPP, PET, PVDC, PA, paper and aluminum foil, and can be used as the protective film for the protection of processing, transportation and storage.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
A preparation method of acrylate pressure-sensitive adhesive for a protective film comprises the steps of taking a polymer A, a polymer B, a compound C and optionally tackifying resin and/or plasticizer as raw materials, mixing according to a formula proportion, and uniformly mixing to obtain the acrylate pressure-sensitive adhesive for the protective film.
Wherein,
firstly, the preparation of the polymer A comprises the following embodiments 1-5:
example 1:
the polymer A is prepared from the following raw materials in parts by weight: 70 parts of acrylate monomer, 12 parts of methacrylate monomer and 3 parts of acrylate monomer; 0.3 part of an initiator; and 100 parts of ethyl acetate. The acrylate monomer is methyl acrylate, the methacrylate monomer is methyl methacrylate, the acrylate monomer is hydroxyethyl acrylate, and the initiator is azobisisobutyronitrile.
Synthesis of Polymer A: adding ethyl acetate into a reaction kettle, starting stirring, adding 20 parts of mixed monomer consisting of the monomers, and simultaneously adding 0.1 part of initiator; heating to 78 deg.C, keeping the temperature for 0.5 h, adding the rest monomer containing 0.2 weight parts of initiator dropwise, and feeding for 3 h; after the addition, the temperature is kept for 60 minutes, and the initiator is replenished every three ten minutes; keeping the temperature for 1.5 hours after the initiator is added, cooling and discharging;
example 2:
the polymer A is prepared from the following raw materials in parts by weight: 65 parts of acrylate monomer and 5 parts of methacrylate monomer; 3 parts of acrylic acid and 15 parts of acrylic hydroxy ester monomer; 0.8 part of an initiator; and 100 parts of ethyl acetate.
Synthesis of Polymer A: adding ethyl acetate into a reaction kettle, starting stirring, adding 20 parts of mixed monomer consisting of the monomers, and simultaneously adding 0.1 part of initiator; heating to 78 deg.C, keeping the temperature for 1 hour, dripping the rest monomer containing 0.3 weight part of initiator, and feeding for 3.5 hours; after the addition, the temperature is kept for 60 minutes, and the initiator is replenished every three ten minutes; keeping the temperature for 1.5 hours after the initiator is added, cooling and discharging.
Example 3:
the polymer A is prepared from the following raw materials in parts by weight: 80 parts of acrylate monomer and 12 parts of methacrylate monomer; 5 parts of acrylic acid and 15 parts of acrylic hydroxy ester monomer; 0.3 part of an initiator; and 100 parts of ethyl acetate.
The synthesis of polymer a was the same as in example 1.
Example 4:
the polymer A is prepared from the following raw materials in parts by weight: 90 parts of acrylate monomer, 3 parts of acrylic acid and 15 parts of acrylic hydroxy ester monomer; 0.3 part of an initiator; and 100 parts of ethyl acetate.
The synthesis of polymer a was the same as in example 1.
Example 5:
the polymer A is prepared from the following raw materials in parts by weight: 82 parts of acrylate monomer and 10 parts of hydroxyl acrylate monomer; 0.3 part of an initiator; and 100 parts of ethyl acetate.
The synthesis of polymer a was the same as in example 1.
Secondly, the preparation of the polymer B comprises examples 6 to 7, which are specifically as follows:
example 6:
the polymer B is prepared from the following raw materials in parts by weight: 89 parts of acrylate monomer and 12 parts of methacrylate monomer; 0.3 part of an initiator; and 100 parts of ethyl acetate. The acrylate monomer is methyl acrylate, and the methacrylate monomer is methyl methacrylate;
synthesis of Polymer B: adding ethyl acetate into a reaction kettle, starting stirring, adding 20 parts of mixed monomer consisting of the monomers, and simultaneously adding 0.1 part of initiator; heating to 78 deg.C, keeping the temperature for 0.5 h, adding the rest monomer containing 0.1 weight part of initiator dropwise, and feeding for 3 h; after the addition, the temperature is kept for 60 minutes, and the initiator is replenished every three ten minutes; keeping the temperature for 1.5 hours after the initiator is added, cooling and discharging;
example 7:
the polymer B is prepared from the following raw materials in parts by weight: 100 parts of acrylate monomer; 0.5 part of an initiator; and 100 parts of ethyl acetate.
The synthesis of polymer B was the same as in example 6.
And thirdly, the compound C is polyoxypropylene diisocyanate, the tackifying resin is rosin, and the plasticizer is dibutyl phthalate.
Fourthly, detecting a product formula table and strength:
the composite base materials are polyester film, polyethylene film, polypropylene film and aluminizer which are processed by corona;
the test method comprises the following steps: uniformly coating on plastic film (such as polyester film) with 12 mm wire bar, blowing water with electric blower, compounding with another polyethylene film to obtain PET/PE composite film, curing in 60 deg.C oven for 24 hr, taking out, sampling and measuring according to GB/T8808.
The initial adhesion, the peeling force and the permanent adhesion are simultaneously detected, and the specific product formula and the detection result are shown in tables 1 to 5
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
Remarking: in tables 1-5, Δ, the film was attached to the mirror plate, cooled to room temperature for 24 hours at 80 ℃ and torn off, and no fog was observed if the glue was removed; the check mark has no fog and does not drop glue; 1m means that the film is placed for one month at normal temperature after being pasted.
As can be seen from tables 1 to 5, the invention has good initial adhesion, peeling force and permanent adhesion, and has the performance similar to rubber type pressure sensitive adhesive.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (6)
1. The acrylate pressure-sensitive adhesive for the protective film is characterized by being mainly prepared from the following raw materials in parts by weight:
100 parts of a polymer A;
5-50 parts of polymer B;
0.2-2 parts of a compound C;
wherein the polymer A is a polymer containing crosslinkable functional groups, and the glass transition temperature of the polymer A is between-10 ℃ and-65 ℃; the polymer A is prepared from the following raw materials in parts by weight: 80-95 parts of acrylate monomer, 5-20 parts of methacrylate monomer or acrylic acid; 0.5-10 parts of acrylate monomers; 0.2-1 part of initiator; 100 portions of ethyl acetate and 150 portions of polymer B, wherein the polymer B is a polymer without crosslinkable functional groups and is prepared from the following raw materials in parts by weight: 60-100 parts of acrylate monomer; 1-15 parts of a methacrylate monomer; 0.2-1 part of initiator; 100 portions of ethyl acetate and 150 portions of ethyl acetate; the compound C is an amino-containing compound, a polyvalent metal compound or an isocyanate-containing compound; the compound containing amino is polyamine; the isocyanate group-containing compound is a compound containing two or more blocked isocyanate groups.
2. The acrylate pressure-sensitive adhesive for protective films according to claim 1, characterized in that: the acrylate monomer is one or more than two of methyl acrylate, ethyl acrylate, butyl acrylate and isooctyl acrylate.
3. The acrylate pressure-sensitive adhesive for protective films according to claim 1, characterized in that: the methacrylate monomer is one or more than two of methyl methacrylate, ethyl methacrylate and butyl methacrylate.
4. The acrylate pressure-sensitive adhesive for protective films according to claim 1, characterized in that: the acrylate pressure-sensitive adhesive for the protective film also comprises tackifying resin and/or plasticizer, wherein the using amount of the tackifying resin is 1-30 parts by weight, and the using amount of the plasticizer is 1-10 parts by weight.
5. The method for preparing the acrylate pressure-sensitive adhesive for protective films according to claim 1, characterized by comprising the steps of:
1) synthesis of Polymer A: adding ethyl acetate into a reaction kettle, starting stirring, adding 20 parts of mixed monomer consisting of acrylate monomer and methacrylate monomer or acrylic acid and acrylic hydroxy ester monomer, and simultaneously adding 0.1 part of initiator; heating to 78 deg.C, maintaining for 0.5-1 hr, and adding the rest mixed monomer containing 0.2-0.4 weight parts of initiator for 3-3.5 hr; after the addition is finished, the temperature is kept for 60 minutes, and the initiator is added every thirty minutes; keeping the temperature for 1.5 hours after the initiator is added, cooling and discharging;
2) synthesis of Polymer B: adding ethyl acetate into a reaction kettle, starting stirring, adding 20 parts of mixed monomer consisting of acrylate monomer and methacrylate monomer, and simultaneously adding 0.1 part of initiator; heating to 78 deg.C, maintaining for 0.5-1 hr, and adding the rest mixed monomer containing 0.2-0.4 weight parts of initiator for 3-3.5 hr; after the addition is finished, the temperature is kept for 60 minutes, and the initiator is added every thirty minutes; keeping the temperature for 1.5 hours after the initiator is added, cooling and discharging;
3) mixing the polymer A prepared in the step 1), the polymer B prepared in the step 2) and the compound C according to the proportion in the claim 1, and uniformly mixing to obtain the acrylate pressure-sensitive adhesive for the protective film.
6. The method for preparing the acrylate pressure-sensitive adhesive for protective films according to claim 5, comprising the steps of: in step 3, the acrylate pressure-sensitive adhesive for the protective film further comprises tackifying resin and a plasticizer, wherein the using amount of the tackifying resin is 1-30 parts by weight, and the using amount of the plasticizer is 1-10 parts by weight.
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| CN108795342A (en) * | 2018-06-20 | 2018-11-13 | 烟台保立佳新材料有限公司 | A kind of polyethylene protective film pressure sensitive adhesive and its preparation process that can eliminate fisheye |
| CN109536048A (en) * | 2018-10-11 | 2019-03-29 | 福建鸿利印刷材料工贸有限公司 | A kind of environmental protection composite membrane and its glue and preparation method that use |
| CN111866670B (en) * | 2019-04-24 | 2022-04-22 | 歌尔股份有限公司 | Vibrating diaphragm for miniature sound generating device and miniature sound generating device |
| CN111866671B (en) * | 2019-04-24 | 2021-11-16 | 歌尔股份有限公司 | Vibrating diaphragm for miniature sound generating device and miniature sound generating device |
| CN110041860B (en) * | 2019-05-14 | 2020-11-13 | 平湖铂淳胶粘技术股份有限公司 | Pressure-sensitive adhesive with high peeling force and preparation method thereof |
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| CN1174224A (en) * | 1996-07-18 | 1998-02-25 | 日东电工株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheets |
| CN101331202A (en) * | 2005-12-14 | 2008-12-24 | Lg化学株式会社 | Acrylic pressure-sensitive adhesive compositions |
| CN102260477A (en) * | 2010-12-14 | 2011-11-30 | 上海凯鑫森产业投资控股有限公司 | Pressure-sensitive adhesive for biaxially-oriented polypropylene (BOPP) protective film and preparation method thereof |
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| JP2000109771A (en) * | 1998-10-07 | 2000-04-18 | Lintec Corp | Adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1174224A (en) * | 1996-07-18 | 1998-02-25 | 日东电工株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheets |
| CN101331202A (en) * | 2005-12-14 | 2008-12-24 | Lg化学株式会社 | Acrylic pressure-sensitive adhesive compositions |
| CN102260477A (en) * | 2010-12-14 | 2011-11-30 | 上海凯鑫森产业投资控股有限公司 | Pressure-sensitive adhesive for biaxially-oriented polypropylene (BOPP) protective film and preparation method thereof |
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