CN109627996B - High-light-transmittance optical transparent adhesive for attaching touch screen and synthetic method thereof - Google Patents
High-light-transmittance optical transparent adhesive for attaching touch screen and synthetic method thereof Download PDFInfo
- Publication number
- CN109627996B CN109627996B CN201811350586.9A CN201811350586A CN109627996B CN 109627996 B CN109627996 B CN 109627996B CN 201811350586 A CN201811350586 A CN 201811350586A CN 109627996 B CN109627996 B CN 109627996B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- transparent adhesive
- optical transparent
- attaching
- touch screen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000002834 transmittance Methods 0.000 title claims abstract description 48
- 230000003287 optical effect Effects 0.000 title claims abstract description 45
- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- 238000010189 synthetic method Methods 0.000 title description 2
- 239000002994 raw material Substances 0.000 claims abstract description 51
- 239000003999 initiator Substances 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- -1 (methyl) acrylic acid hydroxyalkyl ester Chemical class 0.000 claims abstract description 23
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 14
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 84
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 46
- 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 43
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 30
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 27
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 26
- 230000018044 dehydration Effects 0.000 claims description 24
- 238000006297 dehydration reaction Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002808 molecular sieve Substances 0.000 claims description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 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 18
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 18
- 208000005156 Dehydration Diseases 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 15
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 11
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 11
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 9
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 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
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- NCTBYWFEJFTVEL-UHFFFAOYSA-N 2-methylbutyl prop-2-enoate Chemical compound CCC(C)COC(=O)C=C NCTBYWFEJFTVEL-UHFFFAOYSA-N 0.000 claims description 2
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 2
- BVDBXCXQMHBGQM-UHFFFAOYSA-N 4-methylpentan-2-yl prop-2-enoate Chemical compound CC(C)CC(C)OC(=O)C=C BVDBXCXQMHBGQM-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-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
- 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 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 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
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 230000002335 preservative effect Effects 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 239000002313 adhesive film Substances 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 26
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 23
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009472 formulation Methods 0.000 description 10
- 238000007599 discharging Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- PQJYXFVJBSRUPG-UHFFFAOYSA-N [3-(2-methylaziridine-1-carbonyl)phenyl]-(2-methylaziridin-1-yl)methanone Chemical compound CC1CN1C(=O)C1=CC=CC(C(=O)N2C(C2)C)=C1 PQJYXFVJBSRUPG-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a high-light-transmittance optical transparent adhesive for attaching a touch screen and a synthesis method thereof. The raw material formula of the high-light-transmittance optical transparent adhesive comprises, by weight, 30-50 parts of (methyl) acrylic acid alkyl ester, 25-40 parts of (methyl) acrylic acid hydroxyalkyl ester, 1-3 parts of N atom-containing polar monomer, 10-20 parts of cross-linking agent, 0.01-0.02 part of chain transfer agent and 0.5-1 part of thermal initiator. The high-light-transmittance optical transparent adhesive disclosed by the invention is in a pressure-sensitive state after being subjected to thermosetting, has moderate initial adhesion and excellent permanent adhesion, is not displaced and not easy to fall off after being attached, has the light transmittance of over 99.5%, the haze value of less than 0.1%, the refractive index close to the refractive index of glass of 1.49, and is environment-friendly in synthesis method.
Description
Technical Field
The invention belongs to optical adhesives, and particularly relates to a high-light-transmittance optical transparent adhesive for attaching a liquid crystal display screen and a synthesis method thereof.
Background
At present, the smart phone and the flat panel market mostly adopt a direct attaching technology to eliminate a gap between an LCM (liquid crystal module) and a touch screen glass or a film. Most contact panel factories are used to adopt an OCA (optical adhesive tape) laminating technology with high production efficiency and uniform thickness when glass laminating is carried out, the OCA has a great property relation with the OCA, is suitable for the condition that the laminating surface of the OCA is smaller such as a mobile phone, a flat plate and the like, has high production efficiency, and is particularly suitable for thermosetting the OCA, can be cured by heating to prepare an adhesive film, so that the application is convenient and quick.
The UV curing OCA requires ultraviolet light irradiation, but because the frame portion of the touch panel is printed with opaque ink, the ultraviolet light cannot penetrate through the ink to irradiate the areas, so that uncured areas are generated, and complete curing cannot be ensured even if the areas are additionally irradiated by side light sources, which greatly increases the equipment cost and reduces the production efficiency.
Currently, OCA is mainly provided in the united states, japan and korea, the united states mainly provides 3M, japan mainly provides ponding, Nitto, prince, hitachi, and dayrong, and korea mainly provides LGH (a subsidiary of LG), but these companies open high-performance products that are basically kept secret.
The Chinese invention patent application CN107057612A (2017.08.18) discloses a high-light-transmittance acrylic pressure-sensitive adhesive and a preparation method thereof, wherein the acrylic pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: 0-30 parts of cohesive monomer, 50-75 parts of viscous monomer, 1-10 parts of functional monomer, 5-10 parts of o-phenylphenoxyethyl acrylate, 0.3-0.8 part of initiator, 100-150 parts of solvent and 0.1-0.5 wt% of curing agent. The high-light-transmittance acrylate pressure-sensitive adhesive provided by the invention has very high transmittance (the light transmittance is more than or equal to 93%), no adhesive residue phenomenon under normal use and treatment, high peel strength, no degumming and adhesive layer and interface damage phenomenon in the use process, and well solves the bonding problem in the fields of aerospace, electronics and electricity, LCD, PDP, OLED and other optical devices. However, the performance of the pressure-sensitive adhesive obtained by the technology needs to be improved, for example, the light transmittance is only 93% -96%, while the light transmittance of the OCA optical adhesive required by the current high-end equipment needs to be more than 99%, possibly due to process problems and lack of special monomers; secondly, the initial adhesion of the pressure-sensitive adhesive obtained by the technology is higher than that of a No. 10 steel ball, the initial adhesion of an international high-end OCA adhesive film is generally a No. 6 steel ball, the initial use of the adhesive film is seriously influenced due to overlarge initial adhesion, great inconvenience is brought to the production of the electronic equipment industry, the adhesive film is too soft, the proportion of soft and hard monomers is improper, the molecular weight and the crosslinking degree of the prepolymer are insufficient, the molecular weight is too small, and the initial adhesion is large. The pressure-sensitive adhesive obtained by the third technology has over-small permanent adhesive force of over 72 hours, while the permanent adhesive force of a high-end adhesive film needs to be over 240 hours, otherwise, the pressure-sensitive adhesive is easy to fall off in the using process. Fourth, the conventional technique uses a common functional monomer acrylic acid, which has a strong acidity, and when an optical adhesive containing the monomer is used for bonding an optical device containing an electrode, such as a touch panel, the electrode is corroded.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides the high-light-transmittance optical transparent adhesive for attaching the touch screen, which has the advantages of light transmittance of over 99.5 percent, haze value of less than 0.1 percent, refractive index close to that of glass of 1.49, moderate initial adhesion, excellent permanent adhesion, environmental friendliness and a thermosetting function, and a synthesis method thereof.
The optical transparent adhesive is in a thermosetting form, and the synthesized prepolymer is coated on a release film to form a BAB type interlayer structure, wherein B is the release film, and A is an adhesive film. Then through the vacuum drying oven, the glued membrane thermosetting, when using, uncover from the type membrane both can carry out the screen laminating, convenient to use.
1) The effect of hydrophilic hydroxyl in the hydroxyalkyl acrylate is utilized, and the high molecular weight cross-linking agent is matched, so that only trace water vapor in the adhesive film is uniformly dispersed, and cloud point cannot be formed, so that the light transmittance is improved again, the haze is reduced, the high molecular weight cross-linking agent has a larger refractive index, and the light transmittance is improved to a great extent (the high refractive index is closer to the refractive index of the base material, and the light loss is reduced); the optical performance indexes of the adhesive film obtained by the invention are far better than those of the current domestic optical transparent adhesive film.
2) The water vapor has great influence on the light transmittance and the haze of the adhesive film, and when the light transmittance reaches more than 90 percent, the important reason for influencing the light transmittance and the haze of the system is a small amount of water vapor in the system; the raw materials are subjected to pre-dehydration treatment to remove most of water vapor, so that the moisture which is little in the system but has great influence on the light transmittance and the haze is greatly reduced, and the light transmittance and the haze of the adhesive film can be greatly improved after dehydration.
3) The permanent adhesion and the initial adhesion are opposite performances, and the adhesive film has low cohesive strength due to low molecular weight and crosslinking degree, so that the permanent adhesion is too small; the invention utilizes a monomer containing polar N atoms, uses a cross-linking agent 1, 1' - (1,3 benzene dicarbonyl) -di- (2-methyl aziridine) (bisamide) with large molecular weight, and the N atoms have strong polarity, so that the interaction between molecular chains in a prepolymer is enhanced, and finally, the adhesive film has moderate molecular weight, high cross-linking degree and proper proportion of soft and hard monomers, thereby having moderate initial adhesion and excellent permanent adhesion.
The purpose of the invention is realized by the following technical scheme:
a high-transmittance optical transparent adhesive for attaching a touch screen comprises: the raw material formula comprises, by weight, 30-50 parts of alkyl (meth) acrylate, 25-40 parts of hydroxyalkyl (meth) acrylate, 1-3 parts of polar monomer containing N atom, 10-20 parts of cross-linking agent, 0.01-0.02 part of chain transfer agent, and 0.5-1 part of thermal initiator;
the cross-linking agent is 1, 1' - (1,3 benzenedicarbonyl) -bis- (2-methylazetidine);
the (methyl) acrylic acid alkyl ester is one or more of methyl acrylate, ethyl acrylate, isopropyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, isobornyl acrylate, 2-methylbutyl acrylate, 4-methyl-2-pentyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobornyl methacrylate and butyl methacrylate;
the hydroxyalkyl (meth) acrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the polar monomer containing N atoms is N-alkyl (methyl) acrylamide, N-dialkyl (methyl) acrylamide or N-vinyl lactam;
all raw materials were dehydrated before use.
To further achieve the object of the present invention, preferably, the N-vinyl lactam is one or more of N-vinyl pyrrolidone and N-vinyl caprolactam;
preferably, the chain transfer agent is dodecyl mercaptan.
Preferably, the thermal initiator is azobisisobutyronitrile.
Preferably, the raw material formulation further comprises one or more of inorganic fillers, reactive or non-reactive plasticizers, heat stabilizers, antifoaming agents, preservatives and diluents.
Preferably, the dehydration treatment means that the solid raw material is dehydrated through a vacuum oven; the liquid raw material is dehydrated in vacuum by oil bath and then dehydrated by molecular sieve, if the raw material is solid at normal temperature and is heated, the raw material is liquid, the raw material can be dehydrated in vacuum oil bath and then dehydrated by molecular sieve in liquid state.
Preferably, the vacuum oven dehydration is to place the solid substance in a vacuum oven at 50-80 ℃ for 12-24h to remove water vapor before use; the oil bath vacuum dehydration is to control the temperature of an oil bath kettle to be 0-10 ℃ higher than the boiling point temperature of the monomer, dehydrate for 1-3h and reduce the temperature.
Preferably, the molecular sieve is a natural zeolite or synthetic zeolite molecular sieve with the model of 3A, 4A, 5A, 10Z, 13Z, Y or sodium mordenite type molecular sieve.
The synthesis method of the high-transmittance optical transparent adhesive for attaching the touch screen comprises the following steps:
1) dehydrating the monomers and the cross-linking agent in the raw materials in vacuum according to respective boiling points, wherein the temperature of an oil bath pot is 0-10 ℃ higher than the temperature of the monomers, the dehydration time is 1-3h, dehydrating all the monomers and the solvents for 12-36h by using a molecular sieve respectively after cooling, removing the molecular sieve for later use, and placing the solid substances in a vacuum oven at 50-80 ℃ for 12-24h to remove water vapor before use;
2) adding alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, a polar monomer containing an N atom, and a chain transfer agent, adding a solvent, and heating to 70-90 ℃;
3) in the temperature rising process, dissolving an initiator in a solvent and adding;
4) after finishing the dripping of the initiator, heating to 70-90 ℃ for continuous reaction for 4-6h, then cooling to 35-50 ℃, adding a mixture of a cross-linking agent and a solvent, keeping for 20-40min, and cooling to obtain a liquid pressure-sensitive adhesive;
5) coating the liquid pressure-sensitive adhesive on a release film by a coating machine, passing through a drying tunnel, and then attaching another layer of release film to form the BAB type OCA optical transparent adhesive.
Preferably, the solvent is Ethyl Acetate (EA), acetone or absolute ethanol.
In the raw materials of the invention, the initiator is solid, the majority of other substances are liquid, but part of monomers are solid at room temperature, and the monomers are liquid after oil bath heating, the melting point is generally not high and is at most about 60 ℃, so that the influence on the molecular sieve caused by high temperature is avoided. More particularly, the chain transfer agent dodecyl mercaptan (NDM) is in liquid state, the dosage in the embodiment is very small (1-2 drops, weight is 0.1g), the purity is very high, and further dehydration cannot be performed basically, so that the chain transfer agent dodecyl mercaptan can not be dehydrated by oil bath vacuum and molecular sieve, and can be placed in an oven before use, and can be dehydrated by oil bath vacuum if the dosage is larger in practical application.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the effect of hydrophilic hydroxyl in the hydroxyalkyl acrylate is utilized, and the high molecular weight cross-linking agent is matched, so that only trace water vapor in the adhesive film is uniformly dispersed, and cloud point cannot be formed, so that the light transmittance is improved again, the haze is reduced, the high molecular weight cross-linking agent has a larger refractive index, and the light transmittance is improved to a great extent (the high refractive index is closer to the refractive index of the base material, and the light loss is reduced); the light transmittance of the adhesive film obtained by the invention is over 99.5%, the haze value is lower than 0.1%, the refractive index is close to the glass refractive index of 1.49, and the important optical performance indexes are far better than that of the current domestic optical transparent adhesive.
2) The water vapor has great influence on the light transmittance and the haze of the adhesive film, and when the light transmittance reaches more than 90 percent, the important reason for influencing the light transmittance and the haze of the system is a small amount of water vapor in the system; the raw materials are subjected to pre-dehydration treatment to remove most of water vapor, so that the moisture which is little in the system but has great influence on the light transmittance and the haze is greatly reduced, and the light transmittance and the haze of the adhesive film can be greatly improved after dehydration.
3) The permanent adhesion and the initial adhesion are opposite performances, and the adhesive film has low cohesive strength due to low molecular weight and crosslinking degree, so that the permanent adhesion is too small; the invention utilizes a monomer containing polar N atoms, uses a cross-linking agent 1, 1' - (1,3 benzene dicarbonyl) -di- (2-methyl aziridine) (bisamide) with large molecular weight, and the N atoms have strong polarity, so that the interaction between molecular chains in a prepolymer is enhanced, and finally, the adhesive film has moderate molecular weight, high cross-linking degree and proper proportion of soft and hard monomers, thereby having moderate initial adhesion and excellent permanent adhesion.
4) The monomer and the solvent used in the invention are thermosetting, the equipment is simple, and the optical adhesive is convenient to use after being prepared into an adhesive film.
5) The adhesive film prepared by the invention is a pressure-sensitive adhesive, has moderate initial adhesion, can not generate displacement during the lamination, has a lamination process similar to the prior process, and does not need to add new equipment.
6) After the adhesive film is subjected to the laminating process, the adhesive film can be further cured, so that the adhesive strength is greatly enhanced, and the adhesive film is prevented from falling off.
7) The prior art in the field often uses a functional monomer acrylic acid which has strong acidity, and when the optical adhesive containing the monomer is used for adhering optical devices containing electrodes, such as touch screens, the electrodes are corroded. According to the invention, the monomer containing polar N atoms is used as a functional monomer to replace acrylic acid, so that the mechanical property of the adhesive film is not affected, the prepared adhesive film does not corrode an electrode due to the fact that the adhesive film contains an acidic monomer, and the problem of corrosivity of raw materials in production in the field is solved well.
8) In the prior art, peroxide is often used as an initiator, and the peroxide can generate serious yellow edge after being placed for a long time, so that the appearance, the light transmittance, the haze and other optical properties are seriously influenced; the formula of the invention does not use peroxide as an initiator, and can really realize ultrahigh light transmittance and ultralow haze.
Detailed Description
For better understanding of the present invention, the present invention will be further described with reference to the following examples, but the embodiments of the present invention are not limited thereto.
In the invention, BA is butyl acrylate, HEA is hydroxyethyl acrylate, IBOMA is isobornyl methacrylate, MMA is methyl methacrylate, MA is methyl acrylate, NVP is N-vinyl pyrrolidone, NVC is N-vinyl caprolactam, NDM is dodecyl mercaptan, EA is ethyl acetate, and AIBN is azobisisobutyronitrile.
The optical adhesive prepolymer is uniformly coated on a release film by a film coater, and then another release film is covered to form a BAB type adhesive film, wherein B is the release film, A is the optical adhesive film, and then the BAB type adhesive film is thermally cured by a vacuum drying oven, and when the adhesive is used, the adhesive can be attached by tearing off the release film.
The transmittance was measured using a Lambda950 type UV-visible spectrophotometer, and the film thickness was 50 μm. The refractive index was measured by using an Abbe refractometer, and the haze was measured by using a haze meter. The initial adhesion test uses an initial adhesion tester with the model of CZY-G, the holding adhesion test uses a holding adhesion tester with the model of CZY-GS, the 180-degree peeling force test uses a universal tensile machine, and the film width is 25 mm.
Example 1 (E1): the raw material formula is shown in table 1
Table 1 example 1 raw material formulation table
| Raw materials | BA | HEA | IBOMA | NVP | NDM | EA | AIBN | Acetone (II) | Bisamides | Anhydrous ethanol |
| Mass/g | 20 | 20 | 5 | 1 | 0.1 | 70 | 0.4 | 4 | 8 | 10 |
Pretreatment of raw materials: butyl Acrylate (BA), hydroxyethyl acrylate (HEA), isobornyl methacrylate (IBOMA), N-vinyl pyrrolidone (NVP) and a cross-linking agent bisamide are dehydrated for 1h in vacuum before use, the temperature of an oil bath kettle is the same as the respective boiling point, then the monomers (BA, HEA, IBOMA, NVP), the cross-linking agent bisamide and a solvent Ethyl Acetate (EA) are adsorbed and dehydrated for 12h by a type 3A molecular sieve, and dodecyl mercaptan (NDM) and azobisisobutyronitrile AIBN are placed in a vacuum oven for 12h for standby.
Adding the pretreated BA, HEA, IBOMA, NVP and NDM into a 500ml four-neck flask according to the given amount of the formula, adding 55gEA, mechanically stirring with a digital display function in an experimental device, a condensing device and a thermometer at the rotating speed of 60r/min, heating in an oil bath pan, and gradually heating to 70 ℃ (the temperature is shown by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, shaking uniformly, adding the initiator solution into a polytetrafluoroethylene constant-pressure dropping funnel, and dropping the initiator solution when the temperature in the flask reaches 70 ℃, wherein the dropping process of the initiator solution is about 1 hour. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 70 ℃ for continuous reaction for 6 hours. Then, the temperature in the flask was lowered to 35 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. And finishing dropping within about 20min, continuously reacting for 20min, cooling and discharging.
Example 2 (E2): the raw material formula is shown in Table 2
Table 2 example 2 formulation table
| Raw materials | BA | HPA | MMA | NMMA | NDM | EA | AIBN | Acetone (II) | Bisamides | Anhydrous ethanol |
| Mass/g | 20 | 20 | 5 | 1 | 0.1 | 70 | 0.4 | 4 | 8 | 10 |
Pretreatment of raw materials: BA. Hydroxypropyl acrylate (HPA), Methyl Methacrylate (MMA), N-methyl methacrylamide (NMMA) and a cross-linking agent bisamide are subjected to vacuum dehydration for 2 hours before use, the temperature of an oil bath kettle is 5 ℃ higher than the respective boiling points, then BA, HPA, MMA, NMMA, bisamide, EA, acetone and absolute ethyl alcohol are subjected to adsorption dehydration for 12 hours by a 4A type molecular sieve, and dodecyl mercaptan (NDM) and azobisisobutyronitrile AIBN are placed in a vacuum oven for 12 hours for standby.
Adding the pretreated BA, HPA, MMA, NMMA and NDM into a 500ml four-neck flask according to the amount given by the formula, adding 55gEA, mechanically stirring with a digital display function in an experimental device, a condensing device and a thermometer at the rotating speed of 90r/min, heating in an oil bath pan, and gradually heating to 80 ℃ (the temperature is shown by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, uniformly shaking, adding the initiator solution into a polytetrafluoroethylene constant-pressure dropping funnel, dropwise adding the initiator solution when the temperature in the flask reaches 80 ℃, and carrying out the dropwise adding process of the initiator solution for about 1.5 hours. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 80 ℃ for continuous reaction for 5 hours. Then, the temperature in the flask was lowered to 40 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. And finishing dropping within about 30min, continuously reacting for 30min, cooling and discharging.
Example 3 (E3): the raw material formula is shown in Table 3
Table 3 example 3 formulation table
Pretreatment of raw materials: BA. Hydroxyethyl methacrylate (HEMA), Methyl Acrylate (MA), N-dimethyl methacrylamide (N, N-DMMA) and a cross-linking agent bisamide are dehydrated for 3 hours in vacuum before use, the temperature of an oil bath kettle is 5 ℃ higher than the respective boiling point, then BA, HEMA, MA, N-DMMA, bisamide, EA, acetone and absolute ethyl alcohol are further dehydrated for 36 hours by 5A type molecular sieve adsorption, and dodecyl mercaptan (NDM) and azobisisobutyronitrile AIBN are placed in a vacuum oven for 24 hours for standby.
Adding the pretreated BA, HEMA, MA, N-DMMA and NDM into a 500ml four-neck flask according to the given amount of the formula, adding 55gEA, mechanically stirring an experimental device with a digital display function, a condensing device and a thermometer at the rotating speed of 120r/min, heating the mixture in an oil bath pan, and gradually heating the mixture to 90 ℃ (the temperature is displayed by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, uniformly shaking, adding a polytetrafluoroethylene constant-pressure dropping funnel, dropwise adding the initiator solution when the temperature in the flask reaches 90 ℃, and carrying out the dropwise adding process of the initiator solution for about 2 hours. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 90 ℃ for continuous reaction for 4 hours. Then, the temperature in the flask was lowered to 45 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. And finishing dropping within about 40min, continuously reacting for 30min, cooling and discharging.
Example 4 (E4): the raw material formula is shown in Table 4
Table 4 example 4 formulation table
| Raw materials | BA | HPMA | IBOMA | NVC | NDM | EA | AIBN | Acetone (II) | Bisamides | Anhydrous ethanol |
| Mass/g | 20 | 20 | 5 | 1 | 0.1 | 70 | 0.4 | 4 | 8 | 10 |
Pretreatment of raw materials: BA. Hydroxypropyl methacrylate (HPMA), isobornyl methacrylate (IBOMA), N-vinyl caprolactam (NVC) and a cross-linking agent bisamide are subjected to vacuum dehydration for 2 hours before use, the temperature of an oil bath kettle is 10 ℃ higher than the respective boiling point, then BA, HPMA, IBOMA, NVC, bisamide, EA, acetone and absolute ethyl alcohol are subjected to adsorption dehydration for 24 hours by a 10Z type molecular sieve, and dodecyl mercaptan (NDM) and azobisisobutyronitrile AIBN are placed in a vacuum oven for 24 hours for standby.
Adding the pretreated BA, HPMA, IBOMA, NVC and NDM into a 500ml four-neck flask according to the amount given by the formula, adding 55gEA, mechanically stirring with a digital display function in an experimental device, a condensing device and a thermometer at the rotating speed of 150r/min, heating in an oil bath pan, and gradually heating to 80 ℃ (the temperature is displayed by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, uniformly shaking, adding a polytetrafluoroethylene constant-pressure dropping funnel, dropwise adding the initiator solution when the temperature in the flask reaches 80 ℃, and carrying out the dropwise adding process of the initiator solution for about 2 hours. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 80 ℃ for continuous reaction for 5 hours. Then, the temperature in the flask was lowered to 50 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. And finishing dropping within about 30min, continuously reacting for 40min, cooling and discharging.
Comparative example 1(CE 1): the raw material formula is shown in Table 5
Table 5 table of raw materials formulation of comparative example 1
| Raw materials | BA | MA | NVP | NDM | EA | AIBN | Acetone (II) | Bisamides | Anhydrous ethanol |
| Mass/g | 40 | 5 | 1 | 0.1 | 70 | 0.4 | 4 | 8 | 10 |
Pretreatment of raw materials: BA. MA, NVP and cross-linking agent bisamide are subjected to vacuum dehydration for 3h before use, the temperature of an oil bath pot is 10 ℃ higher than the respective boiling point, then BA, MA, NVP, bisamide, EA, acetone and absolute ethyl alcohol are subjected to adsorption dehydration for 36h by using a 3A type molecular sieve, the consumption of dodecyl mercaptan (NDM) is very small, and the prepared active carbon can be placed in a vacuum oven together with azobisisobutyronitrile AIBN for 24h for standby application.
Adding the pretreated BA, MA, NVP and NDM into a 500ml four-neck flask according to the amount given by the formula, adding 55gEA, mechanically stirring an experimental device with a digital display function, a condensing device and a thermometer at the rotating speed of 60r/min, heating an oil bath pan, and gradually heating to 70 ℃ (the temperature is shown by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, uniformly shaking, adding a polytetrafluoroethylene constant-pressure dropping funnel, dropwise adding the initiator solution when the temperature in the flask reaches 70 ℃, and carrying out the dropwise adding process of the initiator solution for about 1 h. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 70 ℃ for continuous reaction for 6 hours. Then, the temperature in the flask was lowered to 45 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. After the dropwise adding is finished within about 20min, the reaction is continued for 30min, and the temperature is reduced for discharging.
Comparative example 2(CE 2): the raw material formula is shown in Table 6
Table 6 formula of comparative example 2
| Raw materials | BA | HEA | MA | NMMA | NDM | EA | AIBN | Acetone (II) | Bisamides | Anhydrous ethanol |
| Mass/g | 20 | 20 | 5 | 1 | 0.1 | 70 | 0.4 | 4 | 8 | 10 |
The above raw materials are not pretreated.
Adding BA, HEA, MA, NMMA and NDM in a formula table into a 500ml four-neck flask according to the amount given by the formula, adding 55gEA, stirring with a digital display function, a condensing device and a thermometer in an experimental device at a rotation speed of 90r/min, heating in an oil bath pan, and gradually heating to 80 ℃ (the temperature is shown by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, uniformly shaking, adding a polytetrafluoroethylene constant-pressure dropping funnel, dropwise adding the initiator solution when the temperature in the flask reaches 80 ℃, and carrying out the dropwise adding process of the initiator solution for about 1.5 hours. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 80 ℃ for continuous reaction for 5 hours. Then, the temperature in the flask was lowered to 30 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. And finishing dropping within about 30min, continuously reacting for 30min, cooling and discharging.
Comparative example 3(CE 3): the raw material formula is shown in Table 7
Table 7 formula of comparative example 3
| Raw materials | BA | HPA | MMA | NDM | EA | AIBN | Acetone (II) | Bisamides | Anhydrous ethanol |
| Mass/g | 20 | 20 | 5 | 2d | 70 | 0.4 | 4 | 8 | 10 |
Pretreatment of raw materials: BA. HPA, MMA and a cross-linking agent bisamide are subjected to vacuum dehydration for 2 hours before use, the temperature of an oil bath kettle is 5 ℃ higher than the respective boiling point, then BA, HPA, MMA, bisamide, EA, acetone and absolute ethyl alcohol are subjected to adsorption dehydration for 24 hours by using a 4A type molecular sieve, and dodecyl mercaptan (NDM) and azobisisobutyronitrile AIBN are placed in a vacuum oven for 24 hours for standby.
Adding the pretreated BA, HPA, MMA and NDM into a 500ml four-neck flask according to the amount given by the formula, adding 55gEA, mechanically stirring an experimental device with a digital display function, a condensing device and a thermometer at the rotating speed of 120r/min, heating the experimental device in an oil bath, and gradually heating to 80 ℃ (the temperature is displayed by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, uniformly shaking, adding a polytetrafluoroethylene constant-pressure dropping funnel, dropwise adding the initiator solution when the temperature in the flask reaches 80 ℃, and carrying out the dropwise adding process of the initiator solution for about 1.5 hours. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 80 ℃ for continuous reaction for 5 hours. Then, the temperature in the flask was lowered to 40 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. And finishing dropping within about 30min, continuously reacting for 20min, cooling and discharging.
Comparative example 4(CE 4): the raw material formula is shown in Table 8
Table 8 formula of comparative example 4
| Raw materials | BA | HEMA | IBOMA | NVP | NDM | EA | AIBN | Acetone (II) | Anhydrous ethanol |
| Mass/g | 20 | 20 | 5 | 1 | 0.1 | 70 | 0.4 | 4 | 10 |
Pretreatment of raw materials: BA. HEMA, IBOMA, N-DMMA and cross-linking agent bisamide are subjected to vacuum dehydration for 3h before use, the temperature of an oil bath pot is the same as the respective boiling point, then BA, HEMA, IBOMA, NVP, EA, acetone and absolute ethyl alcohol are subjected to adsorption dehydration for 36h by using a 5A type molecular sieve, and dodecyl mercaptan (NDM) and azobisisobutyronitrile AIBN are placed in a vacuum oven for 24h for standby.
Adding the pretreated BA, HEMA, IBOMA, NVP and NDM into a 500ml four-neck flask according to the amount given by the formula, then adding 55gEA, mechanically stirring an experimental device with a digital display function, a condensing device and a thermometer at the rotating speed of 150r/min, heating the experimental device in an oil bath pot, and gradually heating the experimental device to 90 ℃ (the temperature is displayed by the thermometer). And (3) heating, namely dissolving AIBN in acetone, adding the residual EA to form an initiator solution with the concentration of about 0.021g/mL, uniformly shaking, adding a polytetrafluoroethylene constant-pressure dropping funnel, dropwise adding the initiator solution when the temperature in the flask reaches 90 ℃, and carrying out the dropwise adding process of the initiator solution for about 2 hours. After the reaction is finished, the thermometer and the polytetrafluoroethylene constant-pressure funnel are taken down, the nitrogen protection device is added, the nitrogen flow rate is 20mL/s, and the oil bath kettle is kept at 90 ℃ for continuous reaction for 4 hours. Then, the temperature in the flask was lowered to 45 ℃ and a mixed solution of bisamide and absolute ethanol was added dropwise. And finishing dropping within about 40min, continuously reacting for 20min, cooling and discharging.
When the optical and mechanical properties of the adhesive film are tested, the prepolymer is coated on a release film, is thermally cured in a vacuum drying oven, and is transferred to optical glass to be tested by utilizing a Lambda950 type ultraviolet-visible spectrophotometer for light transmittance, an Abbe refractometer is used for testing refractive index, and a haze meter is used for haze. The film thickness after curing was 50 μm.
When mechanical property test is carried out, the prepolymer is coated on a PET film, and is thermally cured for 5min in a vacuum drying oven at 80 ℃, and initial adhesion, permanent adhesion and 180-degree stripping force are tested. The initial adhesion test is carried out according to the initial adhesion test method (rolling ball method) of the GBT4852-2002 pressure-sensitive adhesive tape, the permanent adhesion test is carried out according to the permanent adhesion test method of the GBT4851-1998 pressure-sensitive adhesive tape, and the peeling force test is carried out according to the 180-degree peeling strength test method of the GBT2792-1998 pressure-sensitive adhesive tape.
The optical and mechanical property test results are shown in table 9 below:
TABLE 9 test results of optical properties of various adhesive films
| Item | Light transmittance T% | Haze H% | Refractive index R |
| E1 | 99.5 | 0 | 1.487 |
| E2 | 99.6 | 0.1 | 1.488 |
| E3 | 99.5 | 0 | 1.486 |
| E4 | 99.5 | 0.1 | 1.488 |
| CE1 | 97.3 | 0.5 | 1.480 |
| CE2 | 95.6 | 0.8 | 1.478 |
| CE3 | 99.5 | 0.1 | 1.488 |
| CE4 | 99.6 | 0 | 1.486 |
As can be seen from the test results in Table 9, the optical adhesive films prepared according to all the formulations in the examples have the light transmittance of more than 99.5%, the haze value of less than 0.1% and the refractive index of close to that of glass 1.49, so that the optical properties of the optical adhesive films produced according to the formulations meet the requirements of any industry at present. The main reason is that the water vapor of the system is reduced to be very low by the pretreatment of the raw materials, and in addition, the water vapor only in the system is uniformly dispersed without forming a cloud point when the hydroxyl-containing monomer is used, so that the improvement effect on the optical performance is very large. While comparative examples 1 and 2 have low light transmittance, relatively high haze and relatively low refractive index, and from the observation and analysis of the formulation, it is concluded that comparative example 1 is due to the lack of hydroxyalkyl acrylate, no hydroxyl group in the system, and the inability to uniformly disperse trace amounts of water vapor, thereby forming a cloud point, resulting in a decrease in light transmittance and an increase in haze. In the comparative example 2, the raw materials are not subjected to pre-dehydration treatment, so that the water vapor of the system is more, and the optical performance of the adhesive film is greatly influenced.
From the results of the mechanical property tests in table 10, it can be seen that the initial adhesion of the adhesive films of all the examples is not large, and the value is moderate, so as to meet the industrial requirements, which is the ideal initial adhesion value of the international high-end OCA optical adhesive film. The method mainly comprises the steps of moderate proportion of soft and hard monomers, appropriate dosage of polar monomers containing N atoms and moderate molecular weight and crosslinking degree of the polymer due to the use of the diamide crosslinking agent. In comparative examples 3 and 4, the initial adhesion was as high as 11 and 12, respectively, and the permanent adhesion was too low, and the peel strength was insufficient, mainly because of the lack of a polar monomer containing an N atom in the formulation, too weak interaction between molecular chains, or the lack of a crosslinking agent, too low crosslinking degree of the prepolymer, small molecular weight, insufficient cohesive strength, large initial adhesion, too small permanent adhesion, and insufficient peel strength.
TABLE 10 mechanical Property test results for each sample
It will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof without departing from the scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The utility model provides a touch-sensitive screen laminating is with high luminousness optics clear adhesive which characterized in that: the raw material formula comprises, by weight, 30-50 parts of alkyl (meth) acrylate, 25-40 parts of hydroxyalkyl (meth) acrylate, 1-3 parts of polar monomer containing N atom, 10-20 parts of cross-linking agent, 0.01-0.02 part of chain transfer agent and 0.5-1 part of thermal initiator;
the cross-linking agent is 1, 1' - (1,3 benzenedicarbonyl) -bis- (2-methylazetidine);
the (methyl) acrylic acid alkyl ester is one or more of methyl acrylate, ethyl acrylate, isopropyl acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate, isobornyl acrylate, 2-methylbutyl acrylate, 4-methyl-2-pentyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobornyl methacrylate and butyl methacrylate;
the hydroxyalkyl (meth) acrylate is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the polar monomer containing N atoms is N-alkyl (methyl) acrylamide, N-dialkyl (methyl) acrylamide or N-vinyl lactam;
dehydrating all raw materials before use; the dehydration treatment means that the solid raw material is dehydrated through a vacuum oven; the liquid raw material is dehydrated in vacuum by oil bath and then dehydrated by molecular sieve, if the raw material is solid at normal temperature and is heated, the raw material is liquid, the raw material can be dehydrated in vacuum oil bath and then dehydrated by molecular sieve in liquid state.
2. The high-transmittance optical transparent adhesive for attaching a touch screen according to claim 1, wherein the N-vinyl lactam is one or more of N-vinyl pyrrolidone and N-vinyl caprolactam.
3. The high-transmittance optical transparent adhesive for attaching a touch screen according to claim 1, characterized in that: the chain transfer agent is dodecyl mercaptan.
4. The high-transmittance optical transparent adhesive for attaching a touch screen according to claim 1, characterized in that: the thermal initiator is azobisisobutyronitrile.
5. The high-transmittance optical transparent adhesive for attaching a touch screen according to claim 1, characterized in that: the raw material formula also comprises one or more of inorganic filler, reactive or non-reactive plasticizer, heat stabilizer, defoaming agent, preservative and diluent.
6. The high-transmittance optical transparent adhesive for attaching a touch screen according to claim 1, characterized in that: the vacuum oven dehydration is to place the solid substance in a vacuum oven at 50-80 ℃ for 12-24h to remove water vapor before use; the oil bath vacuum dehydration is to control the temperature of an oil bath kettle to be 0-10 ℃ higher than the boiling point temperature of the monomer, dehydrate for 1-3h and reduce the temperature.
7. The high-transmittance optical transparent adhesive for attaching a touch screen according to claim 1, characterized in that: the molecular sieve is a natural zeolite or synthetic zeolite molecular sieve, and the model is 3A, 4A, 5A, 10Z, 13Z, Y or sodium mordenite type molecular sieve.
8. The method for synthesizing the high-transmittance optical transparent adhesive for attaching the touch screen according to any one of claims 1 to 7, comprising the steps of:
1) dehydrating the monomers and the cross-linking agent in the raw materials in vacuum according to respective boiling points, wherein the temperature of an oil bath pot is 0-10 ℃ higher than the temperature of the monomers, the dehydration time is 1-3h, dehydrating all the monomers and the solvents for 12-36h by using a molecular sieve respectively after cooling, removing the molecular sieve for later use, and placing the solid substances in a vacuum oven at 50-80 ℃ for 12-24h to remove water vapor before use;
2) adding alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, a polar monomer containing an N atom, and a chain transfer agent, adding a solvent, and heating to 70-90 ℃;
3) in the temperature rising process, dissolving an initiator in a solvent and adding;
4) after finishing the dripping of the initiator, heating to 70-90 ℃ for continuous reaction for 4-6h, then cooling to 35-50 ℃, adding a mixture of a cross-linking agent and a solvent, keeping for 20-40min, and cooling to obtain a liquid pressure-sensitive adhesive;
5) coating the liquid pressure-sensitive adhesive on a release film by a coating machine, passing through a drying tunnel, and then attaching another layer of release film to form the BAB type OCA optical transparent adhesive.
9. The method for synthesizing a high-transmittance optical transparent adhesive for attaching a touch screen according to claim 8, wherein the solvent is ethyl acetate, acetone or absolute ethyl alcohol.
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| CN110373122B (en) * | 2019-05-07 | 2021-07-30 | 浙江工业大学 | Interlayer glass intermediate film and preparation method thereof |
| CN110776855B (en) * | 2019-10-31 | 2021-01-19 | 华南理工大学 | UV (ultraviolet) photocuring high-transmittance optical adhesive and preparation method thereof |
| US20220332989A1 (en) * | 2019-12-10 | 2022-10-20 | Lg Chem, Ltd. | Multi-region foldable adhesive film and fabrication method therefor |
| CN112210327A (en) * | 2020-10-12 | 2021-01-12 | 世星科技股份有限公司 | OCA optical cement, preparation method and application thereof |
| CN112195003A (en) * | 2020-10-12 | 2021-01-08 | 世星科技股份有限公司 | OCA optical cement, preparation method and application thereof |
| CN112175553A (en) * | 2020-10-28 | 2021-01-05 | 南京汇鑫光电材料有限公司 | High-refractive-index OCA (optically clear adhesive) |
| CN112552842A (en) * | 2020-11-25 | 2021-03-26 | 江苏皇冠新材料科技有限公司 | Preparation method and application of acrylate pressure-sensitive adhesive |
| CN115216239A (en) * | 2021-05-31 | 2022-10-21 | 江苏斯迪克新材料科技股份有限公司 | Preparation process of optical adhesive tape for electronic product |
| CN115216240A (en) * | 2021-05-31 | 2022-10-21 | 江苏斯迪克新材料科技股份有限公司 | High-transmittance optical adhesive tape |
| CN114381224A (en) * | 2021-12-30 | 2022-04-22 | 无锡万亿星新材料科技有限公司 | High-performance optical pressure-sensitive adhesive applied to folding screen and preparation method thereof |
| CN116333653A (en) * | 2023-03-27 | 2023-06-27 | 太仓斯迪克新材料科技有限公司 | OCA optical cement for bonding vehicle-mounted display screen and preparation method thereof |
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| US20060134362A1 (en) * | 2004-12-17 | 2006-06-22 | 3M Innovative Properties Company | Optically clear pressure sensitive adhesive |
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| KR20130051898A (en) * | 2011-11-10 | 2013-05-21 | 닛토덴코 가부시키가이샤 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
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