WO2022183601A1 - Uv curable pressure-sensitive adhesive - Google Patents
Uv curable pressure-sensitive adhesive Download PDFInfo
- Publication number
- WO2022183601A1 WO2022183601A1 PCT/CN2021/095171 CN2021095171W WO2022183601A1 WO 2022183601 A1 WO2022183601 A1 WO 2022183601A1 CN 2021095171 W CN2021095171 W CN 2021095171W WO 2022183601 A1 WO2022183601 A1 WO 2022183601A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- meth
- pressure
- halogen
- acrylate
- Prior art date
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 57
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 19
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 238000003848 UV Light-Curing Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical group C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- -1 1-hydroxycyclohexyl Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- GRDGBWVSVMLKBV-UHFFFAOYSA-N (2-amino-5-nitrophenyl)-(2-chlorophenyl)methanone Chemical compound NC1=CC=C([N+]([O-])=O)C=C1C(=O)C1=CC=CC=C1Cl GRDGBWVSVMLKBV-UHFFFAOYSA-N 0.000 claims description 2
- ABEVIHIQUUXDMS-UHFFFAOYSA-N (2-bromophenyl)-phenylmethanone Chemical compound BrC1=CC=CC=C1C(=O)C1=CC=CC=C1 ABEVIHIQUUXDMS-UHFFFAOYSA-N 0.000 claims description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 claims description 2
- KEOLYBMGRQYQTN-UHFFFAOYSA-N (4-bromophenyl)-phenylmethanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=CC=C1 KEOLYBMGRQYQTN-UHFFFAOYSA-N 0.000 claims description 2
- OCAJMURFVZWFPX-UHFFFAOYSA-N (4-iodophenyl)-phenylmethanone Chemical compound C1=CC(I)=CC=C1C(=O)C1=CC=CC=C1 OCAJMURFVZWFPX-UHFFFAOYSA-N 0.000 claims description 2
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 claims description 2
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 claims description 2
- LFABNOYDEODDFX-UHFFFAOYSA-N bis(4-bromophenyl)methanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=C(Br)C=C1 LFABNOYDEODDFX-UHFFFAOYSA-N 0.000 claims description 2
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims description 2
- IXOJGFDRZRKILF-UHFFFAOYSA-N 2-(chloromethyl)-1,3,5-triazine Chemical compound ClCC1=NC=NC=N1 IXOJGFDRZRKILF-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000004132 cross linking Methods 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000001029 thermal curing Methods 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 238000005464 sample preparation method Methods 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920002554 vinyl polymer Chemical group 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RBKHNGHPZZZJCI-UHFFFAOYSA-N (4-aminophenyl)-phenylmethanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC=C1 RBKHNGHPZZZJCI-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- XEWQXJJJOIKGTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;octadecanoic acid Chemical compound CC(=C)C(O)=O.CCCCCCCCCCCCCCCCCC(O)=O XEWQXJJJOIKGTP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-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
- IFQUPKAISSPFTE-UHFFFAOYSA-N 4-benzoylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=CC=C1 IFQUPKAISSPFTE-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Chemical class 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 102220501003 Triadin_N75A_mutation Human genes 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical class CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical class CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical class CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
Definitions
- the invention belongs to the technical field of new polymer materials, and particularly relates to a UV-curable pressure-sensitive adhesive.
- PSA Pressure sensitive adhesives
- the traditional (meth)acrylate PSA is cured by thermal crosslinking or UV light curing to improve the shear load resistance.
- the crosslinking (meth)acrylate polymer can effectively improve the shear load capacity of the pressure-sensitive adhesive , but the (meth)acrylate polymer chain structure must contain thermally curable functional groups (such as carboxylic acid, hydroxyl functional groups) or UV-curable functional groups (such as benzophenone, vinyl, or acrylate double bond), during the polymerization process, carboxylic acid, hydroxyl, or benzophenone groups can be introduced into the (meth)acrylate polymer chain structure by copolymerizing with functional group-containing monomers, or in After the polymerization is completed, the vinyl or acrylate double bond group is connected to the polymer main chain through a second chemical reaction.
- the thermal crosslinking process relies on the crosslinking of carboxyl groups and aziridine or hydroxyl and isocyanate. chemical reaction of the agent.
- the main disadvantages of this cross-linking process are: (1) Once the cross-linking agent is added, the PSA formulation begins to undergo a cross-linking reaction, resulting in a continuous increase in the viscosity of the formulation. The service life of the formulation is very short and must be used up within a few hours. ; (2) The cross-linking reaction is relatively slow, and is greatly affected by temperature and humidity, and the problem of incomplete cross-linking often occurs, which causes many difficulties in the quality control of PSA products; (3) As we all know, isocyanate or aziridine etc. The cross-linking agent is highly toxic and poses a safety hazard to the production environment; (4) these thermal cross-linking assistants will reduce the thermal stability and weather resistance of the (meth)acrylate PSA.
- the UV curing process utilizes the photoreaction of UV functional groups to crosslink polymer chains.
- the disadvantages of the existing photocuring methods include: (1) special monomers containing UV functional groups must first be synthesized by separate and complicated steps, and the cost is much more expensive than the general commercialized photoinitiators; (2) Certain UV functional groups, such as acrylate ester double bond groups or vinyl groups, can interfere with the polymerization process of (meth)acrylate PSAs, so they must be introduced into the polymer backbone through a second chemical reaction after the polymerization is complete.
- the reaction is usually very slow and often incomplete; (3) the concentration of UV functional groups of (meth)acrylate polymers is fixed during the polymerization process, and the amount of crosslinking agent in the formulation cannot be adjusted like the thermal curing method. Change the properties of the glue after curing.
- the present application provides a low-cost preparation method, which not only maintains the flexibility of the traditional (meth)acrylate pressure-sensitive adhesive thermal curing formula, but also overcomes the UV curing pressure-sensitive adhesives with the problems of unstable post-curing and short service life.
- a UV-curable pressure-sensitive adhesive is mainly made of the following components by mass percentage:
- a kind of UV curing pressure sensitive adhesive, described halogen-containing photoinitiator is 4-chlorobenzophenone, 4-bromobenzophenone, 4-iodobenzophenone, 4,4' -Dichlorobenzophenone, 4,4'-dibromobenzophenone, 2-chlorobenzophenone, 2-bromobenzophenone, hexachlorobenzene, chloromethyl-1,3,5- One of triazine, chlorothioxanthone, chlorobenzophenone or any mixture.
- the above-mentioned UV-curable pressure-sensitive adhesive further includes 0.01 to 5.0% of a non-halogen photoinitiator.
- UV curing pressure sensitive adhesive described non-halogen photoinitiator is 1-hydroxycyclohexyl phenone, 2,2-dimethoxy-1,2-diphenylethyl-1- Ketone, Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1- Propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinopropan-1-one, and one or any combination of 2-hydroxy-2-methyl-1-phenylpropan-1-one.
- the above-mentioned UV-curable pressure-sensitive adhesive is characterized in that the glass transition temperature of the (meth)acrylate polymer is less than 10° C.; and the average molecular weight is greater than 50,000 g/mol.
- the glass transition temperature of the (meth)acrylate polymer is less than 0°C, and the average molecular weight is greater than 50,000 g/mol.
- UV-curing pressure-sensitive adhesive described UV-curing pressure-sensitive adhesive is obtained by the following method: (meth)acrylate polymerization and halogen light are weighed by the mass number described in the claim. The initiator was mixed with stirring, and the volatile solvent was evaporated under reduced pressure.
- the technical solution provided by the present invention not only maintains the flexibility of the traditional (meth)acrylate pressure-sensitive adhesive thermal curing formula, but also overcomes the problems of unstable post-curing and short service life that exist in thermal curing.
- the technical solution provided by the present invention simplifies the production process of the light-cured pressure-sensitive adhesive while maintaining the advantages of the existing UV light-curing technology, and increases the flexibility of the pressure-sensitive adhesive formulation and the adjustability of its performance.
- the light-curable pressure-sensitive adhesive of the present invention can be made into a product through a coating process and UV light curing, and has a wider application range and better product performance than the existing pressure-sensitive adhesive.
- the 2-ethylhexyl acrylate in this embodiment can also be other (meth)acrylate monomers, and has the following molecular structural formula:
- R1 is H or CH3 and R is an alkyl chain of 1 to 20 carbons.
- Vinyl monomers such as vinyl acetate, styrene, a-methylstyrene, ethyl vinyl ether, acrylonitrile, vinyl pyridine, and vinyl chloride.
- the preparation method of the above-mentioned (meth)acrylate polymer can also carry out according to the technical means of conventional polymerization chemical methods in this area, such as by solution, emulsion or bulk polymerization, such as free radical polymerization, cationic polymerization , anionic polymerization or photopolymerization.
- the polymer can also be further processed by solvent removal, latex coagulation or melt processing to form a solvent-free pressure sensitive adhesive.
- a non-halogen photoinitiator is 1-hydroxycyclohexyl phenone, 2,2-dimethoxy-1,2 -Diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy- 2-Methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropan-1-one, and one or any combination of 2-hydroxy-2-methyl-1-phenylpropan-1-one.
- the pressure-sensitive adhesive was uniformly coated on a polyester film with a thickness of 50 microns by means of hot melt coating, and the coating weight was controlled at 50 g/square meter. Then UV curing was performed in a desktop UV curing machine (medium pressure mercury column, H lamp, 120 W/cm), and the UVC curing dose was controlled at 0.1 J/cm 2 .
- the performance of the pressure-sensitive adhesive was evaluated by the 180° peel force and room temperature adhesion retention test on the stainless steel plate. The bonding time on the steel plate was controlled at 30min and 24h respectively. The sample was 180° peel force and room temperature adhesion. The test conditions and results of the holding force are shown in Table 1.
- ultraviolet rays are crosslinked in air or nitrogen under irradiation with ultraviolet light in the range of 200 to 500 nm.
- Suitable UV radiation sources include carbon arcs, mercury vapor arcs, fluorescent lamps with special ultraviolet light emitting phosphors, electronic flash lamps, and the like, lasers of specific wavelengths, ultraviolet light emitting diodes, and the like.
- Example 1 Example 4 Example 3 Example 4 Example 5 Adhesion retention force (2kg/25mmx25mm), min 1880 1.0 2.5 1.0 3.5 180° stainless steel peel (30min fit), N/25mm 16.7 19.1 19.3 19.2 19.4 180° stainless steel peel (24h fit), N/25mm 19.3 19.7 20.1 19.6 19.5
- Example 1 of the present invention is obviously better than that of Comparative Examples 2 to 5, and Examples 3, 4, and 5 containing other substituted benzophenones are in the same Almost no cross-linking reaction occurred under UV curing conditions, and the adhesion retention was similar to that of Example 2 without photoinitiator.
- a mixture containing 430 g of 2-ethylhexyl acrylate, 240 g of methyl acrylate, 35 g of acrylic acid, 15 g of 2-hydroxyethyl acrylate, and 554 g of ethyl acetate was added to a mixture equipped with a stainless steel stirrer, thermometer, condenser, water bath and slow addition funnel 3 L 4 neck round bottom flask.
- the mixture in the flask was heated to reflux temperature with stirring, and then a mixed solution of 0.4 g of azobisisobutyronitrile and 10 g of ethyl acetate was added to the reaction flask.
- Example 6 of the present invention and Comparative Examples 7 and 8 all have good curing properties and excellent retention, but after the addition of the thermal curing crosslinking agent in Comparative Examples 7 and 8, the formula viscosity began to increase continuously, After 24 hours at room temperature, the degree of cross-linking is too high to be coated.
- the method described in this application is particularly advantageous for the production of UV-curable hot melt pressure sensitive adhesives, and all additives can be added to the copolymer solution at the end of the polymerization reaction. After the solvent is removed, the mixture forms a solvent-free UV-curable hot melt pressure sensitive adhesive.
- additives include but are not limited to one or a combination of the following additives:
- the above-mentioned UV-curable pressure-sensitive adhesive can be mixed with a cross-linking compound to further improve the performance of the pressure-sensitive adhesive product.
- Suitable crosslinking compounds may be multifunctional (meth)acrylate crosslinking agents, specifically, difunctional acrylates or trifunctional acrylates, multifunctional (meth)acrylates, and others capable of crosslinking Difunctional or polyfunctional compounds of acrylic polymers, etc.
- the above UV-curable pressure-sensitive adhesive can be mixed with one or more fillers, such as fibers, carbon black, zinc oxide, titanium dioxide, solid or hollow glass microspheres, microspheres of other materials, silica, silicate and the like.
- fillers such as fibers, carbon black, zinc oxide, titanium dioxide, solid or hollow glass microspheres, microspheres of other materials, silica, silicate and the like.
- the above-mentioned UV-curable pressure-sensitive adhesive can be mixed with commonly used tackifying resins, antioxidants, light stabilizers, adhesion promoters, and the like.
- UV-curable pressure-sensitive adhesive is used to prepare tapes, labels, or other pressure-sensitive adhesive products by any conventional coating method.
- Conventional coating methods include but are not limited to extrusion coating, narrow-mouth coating. , Gravure coating, curtain coating, slot coating, spin coating, screen coating.
- Coated substrates can be in the form of films, tapes, sheets, boards, foams, and the like; and can be made of various substances such as paper, fabric, plastics (polyester, PE, PP, BOPP, and PVC), nonwoven fibers, Made of metal, foil, glass, natural rubber, synthetic rubber, wood or plywood. The enumeration here is not limiting.
- the backside of the substrate is typically coated with a release coating to prevent the adhesive from adhering to the backside of the substrate. If the substrate is to be coated with adhesive on both sides and rolled up, cover the adhesive with a peelable paper or other protector on one side to prevent the adhesive from sticking to the adhesive on the other side mixture. In some applications, the second substrate can be applied directly to the adhesive.
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Abstract
A UV curable pressure-sensitive adhesive, which is prepared from the following components in percentages by mass: a) 95.0 to 99.9% by weight of a (meth)acrylate polymer in which the macromolecular chain does not comprise an ultraviolet light reactive functional group; and b) 0.1 to 5.0% by weight of a halogen-containing photoinitiator, wherein the sum of the weight percentages of the above components is 100%.
Description
本发明属于高分子新材料技术领域，具体涉及一种UV固化压敏胶。The invention belongs to the technical field of new polymer materials, and particularly relates to a UV-curable pressure-sensitive adhesive.
(甲基)丙烯酸酯压敏胶(PSA)因其使用方便、耐用性好、光学性能好、长期使用后可以方便干净地剥离等优点，被广泛应用于各种工业，电子，医疗，交通，和消费产品。随着压敏胶的更广泛使用，对其性能的要求也越来越高。高性能压敏通常要求在较宽的温度范围内，能够承受更长时间和更高的剪切载荷。(Meth)acrylate pressure sensitive adhesives (PSA) are widely used in various industries, electronics, medical, transportation, and consumer products. With the wider use of pressure-sensitive adhesives, the requirements for their performance are also getting higher and higher. High-performance pressure sensitivity typically requires the ability to withstand longer times and higher shear loads over a wider temperature range.
传统的(甲基)丙烯酸酯PSA是通过热交联固化或紫外光固化来提高抗剪切载荷能力，通过交联(甲基)丙烯酸酯聚合物虽然能夠有效提高压敏胶的剪切载荷能力，但是(甲基)丙烯酸酯聚合物链结构中必须含有可热固化的功能团(如羧酸、羟基功能团)或可紫外光固化的功能团(如二苯甲酮基、乙烯基，或丙烯酸酯酯双键)，在聚合过程中，通过与含功能团的单体共聚在(甲基)丙烯酸酯聚合物链结构中可以引入羧酸、羟基，或二苯甲酮基团，或者在聚合完成后，再通过第二次化学反应将乙烯基或丙烯酸酯酯双键基团连接到聚合物主链上，热交联过程依赖于羧基与氮丙啶交联剂或羟基与异氰酸酯交联剂的化学反应。The traditional (meth)acrylate PSA is cured by thermal crosslinking or UV light curing to improve the shear load resistance. Although the crosslinking (meth)acrylate polymer can effectively improve the shear load capacity of the pressure-sensitive adhesive , but the (meth)acrylate polymer chain structure must contain thermally curable functional groups (such as carboxylic acid, hydroxyl functional groups) or UV-curable functional groups (such as benzophenone, vinyl, or acrylate double bond), during the polymerization process, carboxylic acid, hydroxyl, or benzophenone groups can be introduced into the (meth)acrylate polymer chain structure by copolymerizing with functional group-containing monomers, or in After the polymerization is completed, the vinyl or acrylate double bond group is connected to the polymer main chain through a second chemical reaction. The thermal crosslinking process relies on the crosslinking of carboxyl groups and aziridine or hydroxyl and isocyanate. chemical reaction of the agent.
该交联工艺的主要缺点是：(1)一旦加入交联剂后，PSA配方就开始岀现交联反应，导致配方粘度不断增加，配方的使用寿命很短，必须在几个h内用完；(2)交联反应相对较慢，受温度和湿度影响较大，时常出现交联不完全的问题，给PSA产品的质量控制造成很多困难；(3)众所周知，异氰酸酯或叠氮丙啶等交联剂毒性较大，对生产环境造成安全隐患；(4)这些热交联助剂会降低(甲基)丙烯酸酯PSA的热稳定性和耐候性。The main disadvantages of this cross-linking process are: (1) Once the cross-linking agent is added, the PSA formulation begins to undergo a cross-linking reaction, resulting in a continuous increase in the viscosity of the formulation. The service life of the formulation is very short and must be used up within a few hours. ; (2) The cross-linking reaction is relatively slow, and is greatly affected by temperature and humidity, and the problem of incomplete cross-linking often occurs, which causes many difficulties in the quality control of PSA products; (3) As we all know, isocyanate or aziridine etc. The cross-linking agent is highly toxic and poses a safety hazard to the production environment; (4) these thermal cross-linking assistants will reduce the thermal stability and weather resistance of the (meth)acrylate PSA.
紫外光固化过程是利用紫外官能团的光反应交联聚合物链。目前已有光固化方法存在的缺点包括：(1)含UV官能团的特殊单体必须先由单独且复杂的步骤来合成，成本且比一般已商业化的光引发剂昂贵得多；(2)某些UV官能团，如丙烯酸酯酯双键基团或乙烯基会干扰(甲基)丙烯酸酯PSA的聚合过程，因此必须在聚合完成后再通过第二次化学反应引入聚合物主链中，该反应通常是非常缓慢，而且往往反应不完全；(3)(甲基)丙烯酸酯聚合物的紫外官能团浓度是在聚合过程中固定的，不能像热固化方法那样调整配方中交联剂的用量来改变压般胶固化后的性能。The UV curing process utilizes the photoreaction of UV functional groups to crosslink polymer chains. The disadvantages of the existing photocuring methods include: (1) special monomers containing UV functional groups must first be synthesized by separate and complicated steps, and the cost is much more expensive than the general commercialized photoinitiators; (2) Certain UV functional groups, such as acrylate ester double bond groups or vinyl groups, can interfere with the polymerization process of (meth)acrylate PSAs, so they must be introduced into the polymer backbone through a second chemical reaction after the polymerization is complete. The reaction is usually very slow and often incomplete; (3) the concentration of UV functional groups of (meth)acrylate polymers is fixed during the polymerization process, and the amount of crosslinking agent in the formulation cannot be adjusted like the thermal curing method. Change the properties of the glue after curing.
发明内容SUMMARY OF THE INVENTION
针对现有(甲基)丙烯酸酯聚合物固化方法的不足之处，本申请提供一种制备成本低，既保持传统(甲基)丙烯酸酯压敏胶热固化配方的灵活性，又克服了热固化所存在的后固化不稳定的问题以及使用寿命短的问题的UV固化压敏胶。In view of the shortcomings of the existing (meth)acrylate polymer curing methods, the present application provides a low-cost preparation method, which not only maintains the flexibility of the traditional (meth)acrylate pressure-sensitive adhesive thermal curing formula, but also overcomes the UV curing pressure-sensitive adhesives with the problems of unstable post-curing and short service life.
一种UV固化压敏胶，主要由如下质量百分比的组分制成：A UV-curable pressure-sensitive adhesive is mainly made of the following components by mass percentage:
a)95.0至99.9％重量的(甲基)丙烯酸酯聚合物，且其高分子链不含紫外光反应官能团，a) 95.0 to 99.9% by weight of a (meth)acrylate polymer, and its polymer chain does not contain UV light reactive functional groups,
b)0.1至5.0％重量的含卤素光引发剂，b) 0.1 to 5.0% by weight of halogen-containing photoinitiators,
上述组分重量比之和为100％。The sum of the weight ratios of the above components is 100%.
更进一步的，上述的一种UV固化压敏胶，所述的含卤素光引发剂为4-氯二苯甲酮、4-溴代苯甲酮、4-碘苯甲酮、4,4’-二氯二苯甲酮、4,4’-二溴二苯甲酮、2-氯二苯甲酮、2-溴二苯甲酮、六氯苯、氯甲基-1、3,5-三嗪、氯代硫杂蒽酮，氯二苯乙酮的其中之一或者任意混合物。Further, above-mentioned a kind of UV curing pressure sensitive adhesive, described halogen-containing photoinitiator is 4-chlorobenzophenone, 4-bromobenzophenone, 4-iodobenzophenone, 4,4' -Dichlorobenzophenone, 4,4'-dibromobenzophenone, 2-chlorobenzophenone, 2-bromobenzophenone, hexachlorobenzene, chloromethyl-1,3,5- One of triazine, chlorothioxanthone, chlorobenzophenone or any mixture.
更进一步的，上述的-种UV固化压敏胶，还包括0.01至5.0％非卤素光引发剂。Further, the above-mentioned UV-curable pressure-sensitive adhesive further includes 0.01 to 5.0% of a non-halogen photoinitiator.
更进一步的，上述的-种UV固化压敏胶，所述的非卤素光引发剂为1-羟基环己基苯酮、2，2-二甲氧基-1，2-二苯乙-1-酮、双(2，4，6-三甲基苯甲酰基)苯基氧化膦、1-[4-(2-羟基乙氧基)苯基]-2-羟基-2-甲基-1-丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基丙-1-酮，和2-羟基-2-甲基-1-苯基丙-1-酮的其中之一或者任意组合。Further, above-mentioned a kind of UV curing pressure sensitive adhesive, described non-halogen photoinitiator is 1-hydroxycyclohexyl phenone, 2,2-dimethoxy-1,2-diphenylethyl-1- Ketone, Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1- Propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinopropan-1-one, and one or any combination of 2-hydroxy-2-methyl-1-phenylpropan-1-one.
更进一步的，上述的一种UV固化压敏胶，其特征在于，所述(甲基)丙烯酸酯聚合物的玻璃化转变温度小于10℃；平均分子量大于50000g/mol。Further, the above-mentioned UV-curable pressure-sensitive adhesive is characterized in that the glass transition temperature of the (meth)acrylate polymer is less than 10° C.; and the average molecular weight is greater than 50,000 g/mol.
更进一步的，上述的一种UV固化压敏胶，所述的(甲基)丙烯酸酯聚合物的玻璃化转变温度小于0℃，平均分子量大于50000g/mol。Further, in the above-mentioned UV-curable pressure-sensitive adhesive, the glass transition temperature of the (meth)acrylate polymer is less than 0°C, and the average molecular weight is greater than 50,000 g/mol.
更进一步的，上述的一种UV固化压敏胶，所述的UV固化压敏胶通过下述方法制得的：按权利要求所述的质量数称取(甲基)丙烯酸酯聚合和卤素光引发剂，搅拌混合，再减压蒸发挥发性溶剂。Further, above-mentioned a kind of UV-curing pressure-sensitive adhesive, described UV-curing pressure-sensitive adhesive is obtained by the following method: (meth)acrylate polymerization and halogen light are weighed by the mass number described in the claim. The initiator was mixed with stirring, and the volatile solvent was evaporated under reduced pressure.
与现有技术相比，本发明提供的技术方案具有如下技术优点：Compared with the prior art, the technical solution provided by the present invention has the following technical advantages:
1、本发明提供的技术方案既保持传统(甲基)丙烯酸酯压敏胶热固化配方的灵活性，又克服了热固化所存在的后固化不稳定的问题以及使用寿命短的问题。1. The technical solution provided by the present invention not only maintains the flexibility of the traditional (meth)acrylate pressure-sensitive adhesive thermal curing formula, but also overcomes the problems of unstable post-curing and short service life that exist in thermal curing.
2、本发明提供的技术方案在保持现有UV光固化技术优点的同时，简化了光固化压敏胶的生产工艺,增加了压敏胶配方的灵活性和性能的可调性。2. The technical solution provided by the present invention simplifies the production process of the light-cured pressure-sensitive adhesive while maintaining the advantages of the existing UV light-curing technology, and increases the flexibility of the pressure-sensitive adhesive formulation and the adjustability of its performance.
3、本发明的光固化型压敏胶通过涂布工艺和UV光固化做成产品具有比现有压敏胶更广使用范围和更佳产品性能。3. The light-curable pressure-sensitive adhesive of the present invention can be made into a product through a coating process and UV light curing, and has a wider application range and better product performance than the existing pressure-sensitive adhesive.
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施例对本发明的具体实施方式做详细的说明。In order to make the above objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention will be described in detail below with reference to specific embodiments.
实施例1Example 1
称取1080g丙烯酸2-乙基己酯、120g丙烯酸和1100g乙酸乙酯加入配有不锈钢搅拌器、温度计、冷凝器、水浴，和添加漏斗的3000毫升四颈圆底烧瓶中。将烧瓶中的内容物在搅拌条件下加热至回流温度，然后往烧瓶中加入100g乙酸乙酯和4g偶氮二异丁腈(AIBN)混合溶液。继续保持回流240min后，在30min内往烧瓶中加入1g过氧新戊酸叔戊酯和100g乙酸乙酯，并在回流状态下继续反应120min。最后将烧瓶中的反应物冷却至室温。本例所制备的聚合物溶液的固体含量为47.1％，其固体含量为2％时的相对粘度约为2.05。1080 g of 2-ethylhexyl acrylate, 120 g of acrylic acid, and 1100 g of ethyl acetate were weighed into a 3000 ml four-neck round bottom flask equipped with a stainless steel stirrer, thermometer, condenser, water bath, and addition funnel. The contents of the flask were heated to reflux temperature with stirring, and then a mixed solution of 100 g of ethyl acetate and 4 g of azobisisobutyronitrile (AIBN) was added to the flask. After continuing to maintain reflux for 240 min, 1 g of tert-amyl peroxypivalate and 100 g of ethyl acetate were added to the flask within 30 min, and the reaction was continued for 120 min under reflux. Finally the reaction in the flask was cooled to room temperature. The solid content of the polymer solution prepared in this example was 47.1%, and the relative viscosity at 2% solid content was about 2.05.
常温下，将500g上述聚合物溶液与2.35g 4-氯二苯甲酮(每100份丙烯酸酯聚合物中含1.0份4-氯二苯甲酮)混合均匀，然后在减压条件(0.1MPa)下加热至120℃脱挥溶剂。最终的热熔胶样品在150℃时的粘度为41500cps，其固体含量为99.5％。Under normal temperature, 500g of above-mentioned polymer solution and 2.35g of 4-chlorobenzophenone (containing 1.0 part of 4-chlorobenzophenone in every 100 parts of acrylate polymer) were mixed uniformly, and then under reduced pressure (0.1MPa) ) to 120°C to devolatilize the solvent. The final hot melt adhesive sample had a viscosity of 41500 cps at 150°C and a solids content of 99.5%.
需要说明的是：It should be noted:
该实施例中的丙烯酸2-乙基己酯也可以为其它(甲基)丙烯酸酯单体，有如下分子结构式：The 2-ethylhexyl acrylate in this embodiment can also be other (meth)acrylate monomers, and has the following molecular structural formula:
其中R
1为H或CH
3，而R为1个碳到20个碳的烷基链。
wherein R1 is H or CH3 and R is an alkyl chain of 1 to 20 carbons.
具体地说：包括但不限于丙烯酸甲酯、丙烯酸乙酯，甲基丙烯酸乙酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸正戊酯、丙烯酸正己酯、丙烯酸正庚酯、丙烯酸正辛酯、丙烯酸正壬酯、甲基丙烯酸十二酯、丙烯酸环己酯和支化的(甲基)丙烯酸酯异构 体，如丙烯酸异丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯，甲基丙烯酸硬脂酸酯、甲基丙烯酸异辛酯的其中之一或者任意混合。Specifically: including but not limited to methyl acrylate, ethyl acrylate, ethyl methacrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-hexyl acrylate, acrylic acid n-heptyl, n-octyl acrylate, n-nonyl acrylate, dodecyl methacrylate, cyclohexyl acrylate and branched (meth)acrylate isomers such as isobutyl acrylate, n-butyl methacrylate ester, 2-ethylhexyl acrylate, stearate methacrylate, isooctyl methacrylate, or any combination thereof.
也可以为：Can also be:
(甲基)丙烯酸，(甲基)丙烯酸2一羟乙酯、(甲基)丙烯酸4一羟基丁酯、丙烯酰胺、单或二一N一烷基取代的丙烯酰胺、叔丁基丙烯酰胺、二甲基氨基乙基丙烯酰胺、N一辛基丙烯酰胺、聚(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸2一乙氧基乙酯、(甲基)丙烯酸2一甲氧基乙氧基乙酯、甲基丙烯酸2一甲氧基乙酯)、聚乙二醇单(甲基)丙烯酸酯的其中之一或者任意混合。(Meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylamide, mono- or di-N-alkyl substituted acrylamide, tert-butyl acrylamide, Dimethylaminoethyl acrylamide, N-octyl acrylamide, poly(meth)acrylic acid alkoxyalkyl ester, (meth)acrylic acid 2-ethoxyethyl ester, (meth)acrylic acid 2-methyl One of oxyethoxyethyl ester, 2-methoxyethyl methacrylate), polyethylene glycol mono(meth)acrylate or any mixture.
也可以为：Can also be:
乙烯基单体，如乙酸乙烯酯，苯乙烯，a-甲基苯乙烯，乙基乙烯基醚，丙烯腈，乙烯基吡啶，和氯乙烯。Vinyl monomers such as vinyl acetate, styrene, a-methylstyrene, ethyl vinyl ether, acrylonitrile, vinyl pyridine, and vinyl chloride.
上述的(甲基)丙烯酸酯聚合物的制备方法，本领域技术人员也可以根据本领域常规聚合化学方法的技术手段进行，比如可通过溶液、乳液或本体聚合方式，如自由基聚合、阳离子聚合、阴离子聚合或光聚合来制备。所述的聚合物也可以进一步通过去除溶剂、胶乳凝固或熔融处理形成无溶剂压敏胶。The preparation method of the above-mentioned (meth)acrylate polymer, those skilled in the art can also carry out according to the technical means of conventional polymerization chemical methods in this area, such as by solution, emulsion or bulk polymerization, such as free radical polymerization, cationic polymerization , anionic polymerization or photopolymerization. The polymer can also be further processed by solvent removal, latex coagulation or melt processing to form a solvent-free pressure sensitive adhesive.
上述的压敏胶制备过程中，还包括0.01至5.0％非卤素光引发剂，所述的非卤素光引发剂为1-羟基环己基苯酮、2，2-二甲氧基-1，2-二苯乙-1-酮、双(2，4，6-三甲基苯甲酰基)苯基氧化膦、1-[4-(2-羟基乙氧基)苯基]-2-羟基-2-甲基-1-丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基丙-1-酮，和2-羟基-2-甲基-1-苯基丙-1-酮的其中之一或者任意组合。In the preparation process of the above-mentioned pressure-sensitive adhesive, 0.01 to 5.0% of a non-halogen photoinitiator is also included, and the non-halogen photoinitiator is 1-hydroxycyclohexyl phenone, 2,2-dimethoxy-1,2 -Diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy- 2-Methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropan-1-one, and one or any combination of 2-hydroxy-2-methyl-1-phenylpropan-1-one.
压敏胶涂布和UⅤ光固化Pressure Sensitive Adhesive Coating and UV Light Curing
采用热熔涂布的方式将压敏胶均匀地涂在50微米厚的聚酯薄膜上，其涂布量控制在50g/平方米。然后在台式紫外线固化机(中压汞柱，H灯，120瓦/厘米)进行UV固化，其UVC固化剂量控制在0.1焦耳/平方厘米。压敏胶性能通过贴合在不锈钢板上的180°剥离力和室温粘接保持力测试来评定，在钢板上的贴合时间分别控制在30min和24h，该样品180°剥离力和室温粘接保持力的测试条件与结果如表1所示。The pressure-sensitive adhesive was uniformly coated on a polyester film with a thickness of 50 microns by means of hot melt coating, and the coating weight was controlled at 50 g/square meter. Then UV curing was performed in a desktop UV curing machine (medium pressure mercury column, H lamp, 120 W/cm), and the UVC curing dose was controlled at 0.1 J/cm 2 . The performance of the pressure-sensitive adhesive was evaluated by the 180° peel force and room temperature adhesion retention test on the stainless steel plate. The bonding time on the steel plate was controlled at 30min and 24h respectively. The sample was 180° peel force and room temperature adhesion. The test conditions and results of the holding force are shown in Table 1.
更为具体地说，紫外线由200至500nm范围内的紫外光照射下，于空气中或氮气中交联。合适的UV辐射源包括碳弧、汞蒸气弧、具有特殊紫外线发光磷光体的荧光灯、电子闪光灯等、特定波长的激光器、紫外发光二极管等。More specifically, ultraviolet rays are crosslinked in air or nitrogen under irradiation with ultraviolet light in the range of 200 to 500 nm. Suitable UV radiation sources include carbon arcs, mercury vapor arcs, fluorescent lamps with special ultraviolet light emitting phosphors, electronic flash lamps, and the like, lasers of specific wavelengths, ultraviolet light emitting diodes, and the like.
实施例2Example 2
(甲基)丙烯酸酯聚合物中不含光引发剂的比较实施例子。除了压敏胶配方中未使用光引发剂外，其聚合物组成，聚合工艺，和样品制备方法完全如同实施例1，该样品180°剥离力和室温粘接保持力的测试条件与结果如表1所示。Comparative example with no photoinitiator in the (meth)acrylate polymer. Except that the photoinitiator is not used in the pressure-sensitive adhesive formulation, its polymer composition, polymerization process, and sample preparation method are exactly the same as in Example 1. The test conditions and results of the 180° peel force and room temperature adhesion retention force of the sample are shown in the table. 1 shown.
实施例3Example 3
(甲基)丙烯酸酯聚合物中含其它光引发剂的比较实施例子。除了压敏胶中添加了1％重量的苯甲酮取代4-氯二苯甲酮外，其聚合物组成，聚合工艺，和样品制备方法完全如同实施例1，该样品180°剥离力和室温粘接保持力的测试条件与结果如表1所示。Comparative examples of (meth)acrylate polymers containing other photoinitiators. Except that 1% by weight of benzophenone substituted 4-chlorobenzophenone was added to the pressure-sensitive adhesive, its polymer composition, polymerization process, and sample preparation method were exactly the same as those in Example 1. The sample had a 180° peel force and room temperature. The test conditions and results of adhesive retention are shown in Table 1.
实施例4Example 4
(甲基)丙烯酸酯聚合物中含其它光引发剂的比较实施例子。除了压敏胶中添加了1％重量的4-氨基二苯甲酮代替4-氯二苯甲酮外，其聚合物组成，聚合工艺，和样品制备方法完全如同实施例1，该样品180°剥离力和室温粘接保持力的测试条件与结果如表1所示。Comparative examples of (meth)acrylate polymers containing other photoinitiators. Except that 1% by weight of 4-aminobenzophenone was added to replace 4-chlorobenzophenone in the pressure-sensitive adhesive, its polymer composition, polymerization process, and sample preparation method were exactly the same as in Example 1, and the sample was 180° The test conditions and results of peel force and room temperature adhesion retention are shown in Table 1.
实施例5Example 5
(甲基)丙烯酸酯聚合物中含其它光引发剂的比较实施例子。除了压敏胶中添加了1％重量的4-苯甲酰苯甲酸代替4-氯二苯甲酮外，其聚合物组成，聚合工艺，和样品制备方法完全如同实施例1，该样品180°剥离力和室温粘接保持力的测试条件与结果如表1所示。Comparative examples of (meth)acrylate polymers containing other photoinitiators. Except that 1% by weight of 4-benzoylbenzoic acid was added to replace 4-chlorobenzophenone in the pressure-sensitive adhesive, its polymer composition, polymerization process, and sample preparation method were exactly the same as in Example 1, and the sample was 180° The test conditions and results of peel force and room temperature adhesion retention are shown in Table 1.
表1Table 1
| 实施例1Example 1 | 实施例4Example 4 | 实施例3Example 3 | 实施例4Example 4 | 实施例5Example 5 | |
| 粘接保持力(2公斤/25mmⅹ25mm)，minAdhesion retention force (2kg/25mmⅹ25mm), min | 18801880 | 1.01.0 | 2.52.5 | 1.01.0 | 3.53.5 |
| 180°不锈钢剥离(30min贴合)，N/25mm180° stainless steel peel (30min fit), N/25mm | 16.716.7 | 19.119.1 | 19.319.3 | 19.219.2 | 19.419.4 |
| 180°不锈钢剥离(24h贴合)，N/25mm180° stainless steel peel (24h fit), N/25mm | 19.319.3 | 19.719.7 | 20.120.1 | 19.619.6 | 19.519.5 |
根据表1测试结果表明，本发明实施例1的粘接保持力明显优于对比实施例2至5，含有其它取代二苯甲酮的实施例3，实施例4，和实施例5在同样的UV固化条件下几乎没有发生任何交联反应，其粘接保持力与不含光引发剂的实施例2类似。According to the test results in Table 1, the adhesion retention force of Example 1 of the present invention is obviously better than that of Comparative Examples 2 to 5, and Examples 3, 4, and 5 containing other substituted benzophenones are in the same Almost no cross-linking reaction occurred under UV curing conditions, and the adhesion retention was similar to that of Example 2 without photoinitiator.
实施例6Example 6
将含有430g丙烯酸2-乙基己酯、240g丙烯酸甲酯、35g丙烯酸、15g丙烯酸2-羟基乙酯和554g乙酸乙酯的混合物加入配有不锈钢搅拌器、温度计、冷凝器、水浴和慢加漏斗的3升4颈圆底烧瓶中。将烧瓶中的混合物在搅拌条件下加热至回流温度，然后往反应烧瓶加入 0.4g偶氮二异丁腈和10g乙酸乙酯混合溶液。保持回流60min后，再在60min内均匀地向烧瓶中加入0.6g偶氮二异丁腈和50g乙酸乙酯。在回流温度继续聚合反应4h后，然后将1.5g过氧新戊酯和300g乙酸乙酯混合溶液在30min内均地加入聚合反应烧瓶。继续在回流温度反应60min之后，向烧瓶中加入400g乙酸乙酯，将聚合物固含量降低至约33％。本施列聚合物在固体含量为2％时的相对粘度为4.52。A mixture containing 430 g of 2-ethylhexyl acrylate, 240 g of methyl acrylate, 35 g of acrylic acid, 15 g of 2-hydroxyethyl acrylate, and 554 g of ethyl acetate was added to a mixture equipped with a stainless steel stirrer, thermometer, condenser, water bath and slow addition funnel 3 L 4 neck round bottom flask. The mixture in the flask was heated to reflux temperature with stirring, and then a mixed solution of 0.4 g of azobisisobutyronitrile and 10 g of ethyl acetate was added to the reaction flask. After maintaining reflux for 60 min, 0.6 g of azobisisobutyronitrile and 50 g of ethyl acetate were uniformly added to the flask within 60 min. After continuing the polymerization reaction at the reflux temperature for 4 hours, the mixed solution of 1.5 g of peroxypivalate and 300 g of ethyl acetate was uniformly added to the polymerization reaction flask within 30 min. After continuing the reaction at reflux temperature for 60 min, 400 g of ethyl acetate was added to the flask to reduce the polymer solids content to about 33%. The relative viscosity at 2% solids of the present Schneider polymer was 4.52.
将100g上述聚合物溶液与0.33g 4-氯二苯甲酮混合均匀，然后以约每平方米40g干胶涂布量涂在50微米厚的聚酯薄膜上。涂布样品经130℃烘箱烘烤6min后，在台式紫外光固化机(中压汞柱，H灯，120瓦/cm)辐照固化，固化剂量控制在80毫焦/cm
2。压敏胶性能通过贴合在不锈钢板上的180°剥离力和室温粘接保持力测试来评定，在钢板上的贴合时间分别控制在30min和24h，该样品的180°剥离力，室温粘接保持力，胶液的初始粘度室温下24h后的粘度测试结果如表2所示。
100 g of the above polymer solution was mixed well with 0.33 g of 4-chlorobenzophenone, and then coated on a polyester film with a thickness of 50 microns at a dry glue coating weight of about 40 g per square meter. After the coated samples were baked in an oven at 130°C for 6 min, they were irradiated and cured in a desktop UV curing machine (medium pressure mercury column, H lamp, 120 watts/cm 2 ), and the curing dose was controlled at 80 mJ/cm 2 . The performance of the pressure-sensitive adhesive is evaluated by the 180° peel force and the room temperature adhesion retention test on the stainless steel plate. The bonding time on the steel plate is controlled at 30min and 24h respectively. The 180° peel force of the sample, the room temperature adhesion The viscosity test results of the initial viscosity of the glue solution after 24h at room temperature are shown in Table 2.
实施例7Example 7
(甲基)丙烯酸压敏胶采用异氰酸酯交联剂热固化的比较例子。将100g实例6所制备的聚合物溶液与0.1g Desmodur N75A(拜耳生产的多异氰酸酯交联剂)混合均匀后，在50微米厚的聚酯薄膜上涂布样品。在130℃下干燥6min后，涂层干胶重量约为每平方米40g。压敏胶性能通过贴合在不锈钢板上的180°剥离力和室温粘接保持力测试来评定，在钢板上的贴合时间分别控制在30min和24h。该样品的180°剥离力，室温粘接保持力，胶液的初始粘度室温下24h后的粘度测试结果如表2所示。Comparative example of (meth)acrylic pressure-sensitive adhesive thermally cured using an isocyanate crosslinking agent. After mixing 100 g of the polymer solution prepared in Example 6 with 0.1 g of Desmodur N75A (polyisocyanate crosslinking agent produced by Bayer) uniformly, the sample was coated on a polyester film with a thickness of 50 microns. After drying at 130°C for 6 minutes, the dry weight of the coating is about 40g per square meter. The performance of the pressure-sensitive adhesive was evaluated by the 180° peel force and room temperature adhesion retention test on the stainless steel plate, and the bonding time on the steel plate was controlled at 30min and 24h, respectively. The 180° peel force of the sample, the adhesion retention force at room temperature, and the initial viscosity of the glue solution after 24 hours at room temperature are shown in Table 2.
实施例8Example 8
(甲基)丙烯酸压敏胶采用金属螯合交联剂热固化的比较例子。将100g实例6所制备的聚合物溶液与0.1g乙酰丙酮铝(金属螯合交联剂)混合均匀后，在50微米厚的聚酯薄膜上涂布样品。在130℃下干燥6min后，涂层干胶重量约为每平方米40g。压敏胶性能通过贴合在不锈钢板上的180°剥离力和室温粘接保持力测试来评定，在钢板上的贴合时间分别控制在30min和24h。该样品的180°剥离力，室温粘接保持力，胶液的初始粘度室温下24h后的粘度测试结果如表2所示。Comparative example of heat curing of (meth)acrylic pressure sensitive adhesive with metal chelating crosslinking agent. After mixing 100 g of the polymer solution prepared in Example 6 with 0.1 g of aluminum acetylacetonate (metal chelate cross-linking agent) uniformly, the sample was coated on a polyester film with a thickness of 50 microns. After drying at 130°C for 6 minutes, the dry weight of the coating is about 40g per square meter. The performance of the pressure-sensitive adhesive was evaluated by the 180° peel force and room temperature adhesion retention test on the stainless steel plate, and the bonding time on the steel plate was controlled at 30min and 24h, respectively. The 180° peel force of the sample, the adhesion retention force at room temperature, and the initial viscosity of the glue solution after 24 hours at room temperature are shown in Table 2.
表2Table 2
上述结果表明，本发明实施例6和对比实施例7和8均具有良好的固化性能和优越的保持力，但对比实施例7和8在加入热固化交联剂后，配方粘度开始不断增加、室温下放置24h后交联度太高，无法涂布。The above results show that Example 6 of the present invention and Comparative Examples 7 and 8 all have good curing properties and excellent retention, but after the addition of the thermal curing crosslinking agent in Comparative Examples 7 and 8, the formula viscosity began to increase continuously, After 24 hours at room temperature, the degree of cross-linking is too high to be coated.
本申请所述的方法特别有利于生产UV固化热熔压敏胶，所有的添加剂可以在聚合反应的末期加入到共聚物溶液中。在溶剂被去除之后，混合物形成无溶剂UV固化热熔压敏胶。The method described in this application is particularly advantageous for the production of UV-curable hot melt pressure sensitive adhesives, and all additives can be added to the copolymer solution at the end of the polymerization reaction. After the solvent is removed, the mixture forms a solvent-free UV-curable hot melt pressure sensitive adhesive.
其常用添加剂包括但不限于如下添加剂的其中之一或者组合：Its commonly used additives include but are not limited to one or a combination of the following additives:
上述UV固化压敏胶可以混入交联化合物来进一步有提高压敏胶产品的性能。合适的交联化合物的可以是多官能团的(甲基)丙烯酸酯交联剂，具体为，双官能团丙烯酸酯或三官能团丙烯酸酯，多官团(甲基)丙烯酸酯，和其它的能够交联丙烯酸聚合物的双官能或多官能化合物等。The above-mentioned UV-curable pressure-sensitive adhesive can be mixed with a cross-linking compound to further improve the performance of the pressure-sensitive adhesive product. Suitable crosslinking compounds may be multifunctional (meth)acrylate crosslinking agents, specifically, difunctional acrylates or trifunctional acrylates, multifunctional (meth)acrylates, and others capable of crosslinking Difunctional or polyfunctional compounds of acrylic polymers, etc.
上述UV固化压敏胶可以混入一种或多种填料混合，例如纤维、炭黑、氧化锌、二氧化钛、固体或中空玻璃微球、其他材料的微球、二氧化硅、硅酸盐等。The above UV-curable pressure-sensitive adhesive can be mixed with one or more fillers, such as fibers, carbon black, zinc oxide, titanium dioxide, solid or hollow glass microspheres, microspheres of other materials, silica, silicate and the like.
上述UV固化压敏胶可以混入常用的增粘树脂、抗氧化剂、光稳定剂、粘接促进剂等。The above-mentioned UV-curable pressure-sensitive adhesive can be mixed with commonly used tackifying resins, antioxidants, light stabilizers, adhesion promoters, and the like.
再具体应用是，本申请提供的UV固化压敏胶由任何常规涂布方法来制备胶带，标签，或其它压敏胶产品，常规涂布方法包括但不限于挤出涂布，窄口涂布，凹版涂布、窗帘涂布、开槽涂布、旋转涂布、丝网涂布。被涂布的基材可以是膜、带、片、板、泡沫和类似形式；并且可以由各种物质如纸、织物、塑料(聚酯、PE、PP、BOPP和PVC)、无纺纤维、金属、箔、玻璃、天然橡胶、合成橡胶、木材或胶合板制成。这里的列举并不是限制性的。如果带涂层的基材欲以卷状物的形式应用，那么基材的背面通常用防粘涂料来涂覆，以防止粘合剂粘合到基材的背面。如果基材欲在两面均涂布上粘合剂并卷起，那么在一侧将可剥离纸或其它保护物覆盖到粘合剂上，以防止粘合剂粘合于另一侧上的粘合剂。在一些用途中，第二基材可以被直接施用到粘合剂。Another specific application is that the UV-curable pressure-sensitive adhesive provided in this application is used to prepare tapes, labels, or other pressure-sensitive adhesive products by any conventional coating method. Conventional coating methods include but are not limited to extrusion coating, narrow-mouth coating. , Gravure coating, curtain coating, slot coating, spin coating, screen coating. Coated substrates can be in the form of films, tapes, sheets, boards, foams, and the like; and can be made of various substances such as paper, fabric, plastics (polyester, PE, PP, BOPP, and PVC), nonwoven fibers, Made of metal, foil, glass, natural rubber, synthetic rubber, wood or plywood. The enumeration here is not limiting. If the coated substrate is to be applied in roll form, the backside of the substrate is typically coated with a release coating to prevent the adhesive from adhering to the backside of the substrate. If the substrate is to be coated with adhesive on both sides and rolled up, cover the adhesive with a peelable paper or other protector on one side to prevent the adhesive from sticking to the adhesive on the other side mixture. In some applications, the second substrate can be applied directly to the adhesive.
对本发明可以进行许多修改和变化，而不背离其精神和范围，这对于本领域的技术人员将是显而易见的。这里所述的具体实施方案仅仅是通过实施例加以提供，而本发明仅由权利要求以及与之等效的整个范围来限定。Many modifications and variations can be made in the present invention without departing from its spirit and scope, as will be apparent to those skilled in the art. The specific embodiments described herein are provided by way of example only, and the invention is to be limited only by the claims along with their full scope of equivalents.
Claims (7)
- 一种UV固化压敏胶，其特征在于，主要由如下质量百分比的组分制成：A UV-curable pressure-sensitive adhesive is characterized in that, it is mainly made of the following components by mass percentage:a)95.0至99.9％重量的(甲基)丙烯酸酯聚合物，且其高分子链不含紫外光反应官能团，a) 95.0 to 99.9% by weight of a (meth)acrylate polymer, and its polymer chain does not contain UV light reactive functional groups,b)0.1至5.0％重量的含卤素光引发剂，b) 0.1 to 5.0% by weight of halogen-containing photoinitiators,上述组分重量比之和为100％。The sum of the weight ratios of the above components is 100%.
- 根据权利要求1所述的一种UV固化压敏胶，其特征在于，所述的含卤素光引发剂为4-氯二苯甲酮、4-溴代苯甲酮、4-碘苯甲酮、4,4’-二氯二苯甲酮、4,4’-二溴二苯甲酮、2-氯二苯甲酮、2-溴二苯甲酮、六氯苯、氯甲基-1、3,5-三嗪、氯代硫杂蒽酮，氯二苯乙酮的其中之一或者任意混合物。A kind of UV curing pressure sensitive adhesive according to claim 1, is characterized in that, described halogen-containing photoinitiator is 4-chlorobenzophenone, 4-bromobenzophenone, 4-iodobenzophenone , 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, 2-chlorobenzophenone, 2-bromobenzophenone, hexachlorobenzene, chloromethyl-1 , 3,5-triazine, chlorothioxanthone, one or any mixture of chlorobenzophenone.
- 根据权利要求1所述的-种UV固化压敏胶，其特征在于，还包括0.01至5.0％非卤素光引发剂。A kind of UV curing pressure sensitive adhesive according to claim 1, is characterized in that, also comprises 0.01 to 5.0% non-halogen photoinitiator.
- 根据权利要求1所述的-种UV固化压敏胶，其特征在于，所述的非卤素光引发剂为1-羟基环己基苯酮、2，2-二甲氧基-1，2-二苯乙-1-酮、双(2，4，6-三甲基苯甲酰基)苯基氧化膦、1-[4-(2-羟基乙氧基)苯基]-2-羟基-2-甲基-1-丙烷-1-酮、2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)丁酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基丙-1-酮，和2-羟基-2-甲基-1-苯基丙-1-酮的其中之一或者任意组合。A kind of UV curing pressure sensitive adhesive according to claim 1, is characterized in that, described non-halogen photoinitiator is 1-hydroxycyclohexyl phenone, 2,2-dimethoxy-1,2-di Phenethyl-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- Methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone, 2-methyl-1-[4-(methylthio) yl)phenyl]-2-morpholinopropan-1-one, and one or any combination of 2-hydroxy-2-methyl-1-phenylpropan-1-one.
- 根据权利要求1所述的一种UV固化压敏胶，其特征在于，所述(甲基)丙烯酸酯聚合物的玻璃化转变温度小于10℃；平均分子量大于50000g/mol。The UV-curable pressure-sensitive adhesive according to claim 1, wherein the glass transition temperature of the (meth)acrylate polymer is less than 10°C; and the average molecular weight is greater than 50,000 g/mol.
- 根据权利要求1所述的一种UV固化压敏胶，其特征在于，所述的(甲基)丙烯酸酯聚合物的玻璃化转变温度小于0℃，平均分子量大于50000g/mol。The UV-curable pressure-sensitive adhesive according to claim 1, wherein the glass transition temperature of the (meth)acrylate polymer is less than 0°C, and the average molecular weight is greater than 50,000 g/mol.
- 根据权利要求1所述的一种UV固化压敏胶，其特征在于，所述的UV固化压敏胶通过下述方法制得的：按权利要求所述的质量数称取(甲基)丙烯酸酯聚合和卤素光引发剂，搅拌混合，再减压蒸发挥发性溶剂。A kind of UV-curing pressure-sensitive adhesive according to claim 1, is characterized in that, described UV-curing pressure-sensitive adhesive is obtained by the following method: weigh (meth)acrylic acid by the mass number described in the claim The ester polymerization and halogen photoinitiator were mixed with stirring, and then the volatile solvent was evaporated under reduced pressure.
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| CN114392699B (en) * | 2021-12-24 | 2023-04-21 | 东南大学 | Preparation method of high-fluorescence-intensity nano polymer microsphere |
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