JP2005112885A - Active energy ray curing resin composition - Google Patents
Active energy ray curing resin composition Download PDFInfo
- Publication number
- JP2005112885A JP2005112885A JP2003345126A JP2003345126A JP2005112885A JP 2005112885 A JP2005112885 A JP 2005112885A JP 2003345126 A JP2003345126 A JP 2003345126A JP 2003345126 A JP2003345126 A JP 2003345126A JP 2005112885 A JP2005112885 A JP 2005112885A
- Authority
- JP
- Japan
- Prior art keywords
- active energy
- energy ray
- resin composition
- curable resin
- meth
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229920001400 block copolymer Polymers 0.000 claims abstract description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- QHHMCZGPUSLAOG-UHFFFAOYSA-N [Li].FC(S(=O)(=O)C)(F)F Chemical compound [Li].FC(S(=O)(=O)C)(F)F QHHMCZGPUSLAOG-UHFFFAOYSA-N 0.000 claims 1
- -1 poly(alkyl ether) Polymers 0.000 abstract description 17
- 238000005299 abrasion Methods 0.000 abstract description 7
- 125000001979 organolithium group Chemical group 0.000 abstract description 3
- 125000005011 alkyl ether group Chemical group 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 17
- 239000004033 plastic Substances 0.000 description 15
- 229920003023 plastic Polymers 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 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 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
本発明は、紫外線、電子線などの活性エネルギー線により硬化する活性エネルギー線硬化性樹脂組成物に関する。更に詳細には、本発明の活性エネルギー線硬化性樹脂組成物は耐摩耗性、透明性及び帯電防止性に優れた皮膜を形成しうるため、各種プラスチック基材（成型品、フィルム、シートなど）の被覆に適したハードコート剤などの用途に有用である。 The present invention relates to an active energy ray-curable resin composition that is cured by active energy rays such as ultraviolet rays and electron beams. More specifically, since the active energy ray-curable resin composition of the present invention can form a film having excellent wear resistance, transparency and antistatic properties, various plastic substrates (molded products, films, sheets, etc.) It is useful for applications such as a hard coat agent suitable for coating.
一般に、プラスチックは種々の摩擦作用によって傷がつきやすく、また静電気を帯びやすいため大気中に浮遊する微小な粉塵やチリなどが付着しやすいなどの欠点がある。そのため、当該欠点を解消せんとして、これまで多くの改良が試みられてきた。 In general, plastics are easily damaged by various frictional actions, and are susceptible to static electricity, so that fine dust, dust, etc. floating in the atmosphere are likely to adhere. Therefore, many improvements have been attempted so far in order to eliminate the drawbacks.
プラスチックの耐摩耗性を向上させる方法としては、当該プラスチック基材上にハードコート剤を塗布する方法が一般的に採用されている。当該ハードコート剤を塗布した後、紫外線、電子線などの活性エネルギー線を照射して硬化させる方法によれば、当該ハードコート剤塗布層を直ちに硬化させうるため、加工処理スピードが速く、しかも耐摩耗性に優れた硬化皮膜を与えることができるという利点がある。特に、分子中に多くの（メタ）アクリロイル基を有する重合性化合物は高い架橋密度を有するため、当該化合物を含有する活性エネルギー線硬化性樹脂組成物は、プラスチック用の耐摩耗性に優れたハードコート剤として賞用されている。 As a method for improving the wear resistance of a plastic, a method of applying a hard coat agent on the plastic substrate is generally employed. According to the method in which the hard coating agent is applied and then cured by irradiating active energy rays such as ultraviolet rays and electron beams, the hard coating agent coating layer can be immediately cured, so that the processing speed is high and the resistance is high. There exists an advantage that the hardened film excellent in abrasion property can be given. In particular, since a polymerizable compound having many (meth) acryloyl groups in the molecule has a high crosslinking density, the active energy ray-curable resin composition containing the compound is a hard material having excellent wear resistance for plastics. It is used as a coating agent.
このように耐摩耗性に優れた活性エネルギー線硬化性樹脂は周知であるが、耐摩耗性と帯電防止性を同時に満足しうる活性エネルギー線硬化性樹脂は殆ど知られていないのが実情である。活性エネルギー線硬化性樹脂硬化皮膜に帯電防止性能を付与する方法として、活性エネルギー線硬化性樹脂組成物中に界面活性剤、金属粉、カーボンなどを配合することにより、硬化皮膜の表面や内部の導電性を高める方法が実用化されてきた。 Although the active energy ray-curable resin having excellent wear resistance is well known, there are few known active energy ray-curable resins that can simultaneously satisfy the wear resistance and the antistatic property. . As a method of imparting antistatic performance to the active energy ray-curable resin cured film, by adding a surfactant, metal powder, carbon, etc. to the active energy ray-curable resin composition, Methods for increasing conductivity have been put into practical use.
しかし、界面活性剤による導電性の発現には、水分の介在が不可欠であるため、帯電防止能が使用時の湿度に大きく影響されたり、また界面活性剤が表面に移行し脱落しやすいため、当該活性エネルギー線硬化性樹脂組成物を塗工・硬化させてなるプラスチック製品は帯電防止性が長期に持続しないという問題がある。また、金属粉やカーボンを含有する方法では、透明な硬化塗膜が得られないなどの問題がある。 However, since the presence of moisture is indispensable for the expression of conductivity by the surfactant, the antistatic ability is greatly influenced by the humidity during use, or the surfactant is likely to migrate to the surface and fall off, A plastic product obtained by coating and curing the active energy ray-curable resin composition has a problem that antistatic properties do not last for a long time. Further, the method containing metal powder or carbon has a problem that a transparent cured coating film cannot be obtained.
一方、過塩素酸リチウムなどの無機リチウム化合物等のアルカリ金属塩を基材樹脂に添加すると、帯電防止性の樹脂組成物になることが知られている（特許文献１〜４参照）。これらの組成物は、帯電防止性の塗料として利用されており、例えば各種プラスチック基材（成型品、フィルム、シートなど）に塗布され、制電性の光ディスク、成型品などが製造されている。 On the other hand, it is known that when an alkali metal salt such as an inorganic lithium compound such as lithium perchlorate is added to a base resin, an antistatic resin composition is obtained (see Patent Documents 1 to 4). These compositions are used as antistatic paints, and are applied to, for example, various plastic substrates (molded products, films, sheets, etc.) to produce antistatic optical disks, molded products and the like.
しかし、無機リチウム化合物等のアルカリ金属塩を塗料用樹脂に添加する場合、当該アルカリ金属塩が一般的に塗料用樹脂に溶解しにくいため、均一な組成物を調製するのが困難である。また、アルカリ金属塩を重合性モノマーに溶解させる場合、一般的に当該重合性モノマーを加熱する必要があるため、かかる加熱操作によりモノマーの不均一重合が開始するなどして、均一な組成物や塗膜が得られないことがある。一方、アルコール類やエーテル系の溶媒に無機リチウム化合物等のアルカリ金属塩を溶解させる場合、当該アルカリ金属塩が激しく発熱しながら溶解するため、温度制御が困難となることがある。更には、当該アルカリ金属塩のうち特に過塩素酸リチウムなどは腐食性があるため、これらを含有する樹脂組成物を金属表面へ塗布する場合には、防食のための何らかの工夫が必要となるなど、使用に際して制約を伴うことが多い。 However, when an alkali metal salt such as an inorganic lithium compound is added to a coating resin, it is difficult to prepare a uniform composition because the alkali metal salt is generally difficult to dissolve in the coating resin. In addition, when the alkali metal salt is dissolved in the polymerizable monomer, it is generally necessary to heat the polymerizable monomer. Thus, the heating operation starts the heterogeneous polymerization of the monomer, and the uniform composition or A coating film may not be obtained. On the other hand, when an alkali metal salt such as an inorganic lithium compound is dissolved in an alcohol or ether solvent, temperature control may be difficult because the alkali metal salt dissolves with intense heat generation. Furthermore, since lithium perchlorate, among others, is corrosive among the alkali metal salts, when applying a resin composition containing these to a metal surface, some device for anticorrosion is required. In many cases, there are restrictions in use.
上記問題に対し、特定の有機リチウム塩を配合した帯電防止性塗料用組成物が提案されている（特許文献５〜６）。これら特許文献に記載された有機リチウム塩は溶解性に優れるため、リチウムイオンが均一に分散された帯電防止性塗料用組成物が得られる。また、当該有機リチウム塩は、前記の過塩素酸塩などと異なり腐食性がないため、当該有機リチウム塩が配合された帯電防止性塗料用組成物を金属表面に塗布した場合でも、腐食、発錆などの不利がない。 In response to the above problems, antistatic coating compositions containing specific organic lithium salts have been proposed (Patent Documents 5 to 6). Since the organic lithium salt described in these patent documents is excellent in solubility, an antistatic coating composition in which lithium ions are uniformly dispersed can be obtained. In addition, the organolithium salt is not corrosive unlike the above-described perchlorates, and therefore, even when an antistatic coating composition containing the organolithium salt is applied to a metal surface, There are no disadvantages such as rust.
特許文献５〜６に記載された帯電防止性塗料用組成物は、上記のように優れた帯電防止性を有するものであるが耐摩耗性が不十分であるため、塗膜厚みが薄い場合にはハードコート剤として要求される高度の耐摩耗性を発現できない。 The antistatic coating composition described in Patent Documents 5 to 6 has excellent antistatic properties as described above, but has insufficient abrasion resistance, so that the coating thickness is thin. Cannot exhibit the high wear resistance required as a hard coating agent.
本発明は、上記の背景技術に鑑みなされたものであり、その目的は、優れた耐摩耗性及び帯電防止性を有する透明な硬化皮膜を提供しうる、活性エネルギー線硬化性樹脂組成物を提供することにある。 The present invention has been made in view of the above-described background art, and an object thereof is to provide an active energy ray-curable resin composition that can provide a transparent cured film having excellent wear resistance and antistatic properties. There is to do.
本発明者は、前記課題を解決すべく鋭意研究を行った結果、多官能重合性化合物、ポリ（アルキルエーテル）−ポリ（ジメチルシロキサン）ブロック共重合体、および有機リチウム塩からなる活性エネルギー線硬化性樹脂組成物が、プラスチック表面に耐摩耗性及び帯電防止性を同時に満足する透明硬化皮膜を提供できるという知見を得た。本発明は斯かる知見に基づき完成されたものである。 As a result of intensive studies to solve the above problems, the present inventor has made active energy ray curing comprising a polyfunctional polymerizable compound, a poly (alkyl ether) -poly (dimethylsiloxane) block copolymer, and an organic lithium salt. It has been found that the conductive resin composition can provide a transparent cured film that simultaneously satisfies abrasion resistance and antistatic properties on the plastic surface. The present invention has been completed based on such findings.
すなわち本発明は、分子中に少なくとも３つの（メタ）アクリロイル基を有する重合性化合物（Ａ）（以後、（Ａ）成分という）、分子中にアルキルエーテル鎖を有する、ポリ（アルキルエーテル）−ポリ（ジメチルシロキサン）ブロック共重合体（Ｂ）（以後、（Ｂ）成分という）、および有機リチウム塩（Ｃ）（以後、（Ｃ）成分という）を含有する活性エネルギー線硬化性樹脂組成物に係る。 That is, the present invention relates to a polymerizable compound (A) having at least three (meth) acryloyl groups in the molecule (hereinafter referred to as component (A)), a poly (alkyl ether) -poly having an alkyl ether chain in the molecule. An active energy ray-curable resin composition containing a (dimethylsiloxane) block copolymer (B) (hereinafter referred to as component (B)) and an organic lithium salt (C) (hereinafter referred to as component (C)) .
上記構成による本発明の活性エネルギー線硬化性樹脂組成物は、（Ａ）成分に起因して、表面硬度が高く、かつ耐摩耗性に優れた硬化皮膜を提供できる。また、（Ｃ）成分が他の構成成分に対する溶解性に優れるため、リチウムイオンが当該樹脂組成物中に均一に分散され、その結果、透明性に優れた活性エネルギー線硬化性樹脂組成物が得られる。更に、（Ｂ）成分に起因して、硬化皮膜の最表面にリチウムイオン伝導部が形成され、湿度依存性の低くかつ良好な帯電防止性を発現できる。本発明の活性エネルギー線硬化性樹脂組成物が有するこれらの諸特性に基づき、プラスチック基材（成形品、フィルム、シートなど）に適用される従来のコーティング剤が有する問題点、例えば、静電気トラブル、硬化皮膜の傷つきによる審美性の低下などを、悉く解消することができる。 The active energy ray-curable resin composition of the present invention having the above-described configuration can provide a cured film having high surface hardness and excellent wear resistance due to the component (A). In addition, since the component (C) is excellent in solubility in other components, lithium ions are uniformly dispersed in the resin composition, and as a result, an active energy ray-curable resin composition excellent in transparency is obtained. It is done. Furthermore, due to the component (B), a lithium ion conductive portion is formed on the outermost surface of the cured film, and low humidity dependency and good antistatic properties can be expressed. Based on these properties of the active energy ray-curable resin composition of the present invention, problems with conventional coating agents applied to plastic substrates (molded articles, films, sheets, etc.), such as static electricity troubles, A decrease in aesthetics due to a scratch on the cured film can be solved ugly.
本発明の活性エネルギー線硬化性樹脂組成物における（Ａ）成分としては、例えばモノ又はポリペンタエリスリトールポリ（メタ）アクリレートであり、例えばペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、テトラペンタエリスリトールオクタ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエチレンオキサイド変性トリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等が挙げられる。これらはそれぞれを単独でまたは組み合わせて使用できる。なお、分子中に１つまたは２つの（メタ）アクリロイル基を有する重合性化合物を使用した場合には、得られる硬化皮膜の耐摩耗性が不十分となる。 The component (A) in the active energy ray-curable resin composition of the present invention is, for example, mono- or polypentaerythritol poly (meth) acrylate, such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tetrapentaerythritol octa (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide Examples thereof include modified tri (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate. These can be used alone or in combination. In addition, when the polymeric compound which has one or two (meth) acryloyl groups in a molecule | numerator is used, the abrasion resistance of the cured film obtained becomes inadequate.
また（Ａ）成分としては、多官能エポキシ樹脂と（メタ）アクリル酸等との反応により得られる多官能エポキシ（メタ）アクリレート、イソシアネートと水酸基含有（メタ）アクリレート等との反応により得られる多官能ウレタン（メタ）アクリレートなども挙げられ、これら化合物はそれぞれを単独でまたは組み合わせて使用できる。（Ａ）成分の配合量は、活性エネルギー線硬化性樹脂組成物１００質量部あたり、通常６０〜９９質量部程度、好ましくは８０〜９５質量部である。当該配合量が６０質量部より少ない場合には、得られる硬化皮膜の耐摩耗性が不十分となる傾向がある。 Moreover, as (A) component, the polyfunctional epoxy (meth) acrylate obtained by reaction with polyfunctional epoxy resin, (meth) acrylic acid, etc., polyfunctionality obtained by reaction with isocyanate, hydroxyl-containing (meth) acrylate, etc. Urethane (meth) acrylate etc. are also mentioned, and these compounds can be used alone or in combination. (A) The compounding quantity of a component is about 60-99 mass parts normally per 100 mass parts of active energy ray-curable resin compositions, Preferably it is 80-95 mass parts. When the said compounding quantity is less than 60 mass parts, there exists a tendency for the abrasion resistance of the cured film obtained to become inadequate.
（Ｂ）成分は、ポリジメチルシロキサンの側鎖又は末端にポリエチレングリコール鎖、ポリプロピレングリコール鎖等のポリエーテル鎖を有する化合物であり、当該化合物は塗料添加剤としては公知のものである。なお、（Ｂ）成分の代わりに、ポリアルキルエーテル鎖を有しないポリジメチルシロキサンを使用した場合には、本発明におけるような優れた帯電防止性は発現されず、また上記の（Ａ）成分や（Ｃ）成分との相溶性が悪いため、透明な硬化皮膜が得られない。 The component (B) is a compound having a polyether chain such as a polyethylene glycol chain or a polypropylene glycol chain at the side chain or terminal of polydimethylsiloxane, and the compound is known as a paint additive. In addition, when polydimethylsiloxane having no polyalkyl ether chain is used instead of the component (B), the excellent antistatic property as in the present invention is not exhibited, and the component (A) Since the compatibility with the component (C) is poor, a transparent cured film cannot be obtained.
また（Ｂ）成分としては、ウレタン化反応可能な水酸基を有するポリ（アルキルエーテル）−ポリ（ジメチルシロキサン）ブロック共重合体や、活性エネルギー線により重合可能な（メタ）アクリロイル基を有するポリ（アルキルエーテル）−ポリ（ジメチルシロキサン）ブロック共重合体も含まれる。水酸基を有するブロック共重合体は、ウレタン化反応によりポリウレタン（メタ）アクリレートに変性して使用することもできる。（メタ）アクリロイルオキシ基を有するブロック共重合体は、活性エネルギー線照射後の硬化塗膜からのブリードアウト防止効果の点で特に優れている。 As the component (B), a poly (alkyl ether) -poly (dimethylsiloxane) block copolymer having a hydroxyl group capable of urethanation reaction, or a poly (alkyl) having a (meth) acryloyl group that can be polymerized by active energy rays. Ether) -poly (dimethylsiloxane) block copolymers are also included. The block copolymer having a hydroxyl group can be used after being modified into polyurethane (meth) acrylate by a urethanization reaction. The block copolymer having a (meth) acryloyloxy group is particularly excellent in the effect of preventing bleed out from the cured coating film after irradiation with active energy rays.
（Ｂ）成分の配合量は、活性エネルギー線硬化性樹脂組成物１００質量部あたり、通常０.０１〜１０質量部程度、好ましくは０.０５〜５質量部である。当該配合量が０.０１質量部より少ないと、得られる硬化皮膜の帯電防止性が不十分となる傾向があり、また当該配合量が１０質量部を超える場合には、耐摩耗性、プラスチック基材に対する密着性が不十分となる傾向がある。 (B) The compounding quantity of a component is about 0.01-10 mass parts normally per 100 mass parts of active energy ray-curable resin compositions, Preferably it is 0.05-5 mass parts. If the blending amount is less than 0.01 parts by mass, the antistatic property of the resulting cured film tends to be insufficient, and if the blending amount exceeds 10 parts by mass, wear resistance, plastic base There is a tendency for the adhesion to the material to be insufficient.
（Ｃ）成分としては、各種公知の有機リチウム塩から格別限定なく使用できるが、活性エネルギー線硬化性樹脂組成物中の他の構成成分に対する溶解性の観点から、リチウムビス（トリフルオロメタンスルホニル）イミド、リチウム（トリフルオロメタンスルホニル）メタン、及びトリフルオロメタンスルホン酸リチウムからなる群より選択された化合物のうちの少なくとも１種が好ましい。これら例示化合物は、他の構成成分に対する溶解性が格段に優れるため、リチウムイオンが均一に分散された活性エネルギー線硬化性樹脂組成物が得られる。（Ｃ）成分の配合量は、当該組成物１００質量部あたり、通常０．１〜３０質量部程度、好ましくは０．５〜２０質量部である。当該配合量が１質量部より少ないと、得られる硬化皮膜の帯電防止性が不十分と傾向がある。また、当該配合量が３０質量部を超える場合には、得られる硬化皮膜に対する帯電防止性付与効果が飽和するので過剰添加する意義がなく、かえって製品である活性エネルギー線硬化性樹脂組成物のコストが高くなるという不利がある。
As the component (C), various known organic lithium salts can be used without any particular limitation, but from the viewpoint of solubility in other components in the active energy ray-curable resin composition, lithium bis (trifluoromethanesulfonyl) imide. At least one selected from the group consisting of lithium, trifluoromethanesulfonyl) methane, and lithium trifluoromethanesulfonate. Since these exemplary compounds have remarkably excellent solubility in other components, an active energy ray-curable resin composition in which lithium ions are uniformly dispersed can be obtained. (C) The compounding quantity of a component is about 0.1-30 mass parts normally per 100 mass parts of the said compositions, Preferably it is 0.5-20 mass parts. If the amount is less than 1 part by mass, the resulting cured film tends to have insufficient antistatic properties. Moreover, when the said compounding quantity exceeds 30 mass parts, since the antistatic property provision effect with respect to the cured film obtained is saturated, there is no significance of adding excessively, and the cost of the active energy ray curable resin composition which is a product on the contrary Has the disadvantage of becoming higher.
本発明の活性エネルギー線硬化性樹脂組成物は、通常、基材プラスチック表面に塗布された後、活性エネルギー線照射により硬化するが、塗布作業性などの観点から、適宜に有機溶剤で希釈し、所望の粘度に調整して使用することができる。当該有機溶剤としては、硬化性樹脂組成物と混合した場合に均一な溶液を形成しうるものが好ましく、その具体例としては、メタノール、イソプロピルアルコール等のアルコール、トルエン、キシレン等の芳香族炭化水素、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類などが挙げられる。これら有機溶剤は、それぞれ単独または組み合わせて使用することができる。 The active energy ray-curable resin composition of the present invention is usually cured by active energy ray irradiation after being applied to the base plastic surface, but from the viewpoint of application workability, etc., it is appropriately diluted with an organic solvent, It can be used after adjusting to a desired viscosity. The organic solvent is preferably one that can form a uniform solution when mixed with the curable resin composition. Specific examples thereof include alcohols such as methanol and isopropyl alcohol, and aromatic hydrocarbons such as toluene and xylene. , Ketones such as methyl ethyl ketone and methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate. These organic solvents can be used alone or in combination.
本発明の活性エネルギー線硬化性樹脂組成物においては、本発明の目的・作用効果を逸脱しない限り、２官能及び／または単官能の反応性単量体を添加してもかまわない。２官能反応性単量体としては、例えば、テトラエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等のポリエーテルジオールのジ（メタ）アクリレート、１,６−ヘキサンジオールジ（メタ）アクリレート、１,９−ノナンジオールジ（メタ）アクリレート等のポリアルキルジオールのジ（メタ）アクリレート、ビスフェノールＡエチレンオキサイド変性ジ（メタ）アクリレート、シクロヘキサンジオールジ（メタ）アクリレートなどが挙げられる。単官能反応性単量体としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、フェノキシエチルオキシエチル（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、アクリロイルモルホリン、Ｎ−ビニルホルムアミドなどが挙げられる。 In the active energy ray-curable resin composition of the present invention, a bifunctional and / or monofunctional reactive monomer may be added as long as it does not depart from the objects and effects of the present invention. Examples of the bifunctional reactive monomer include di (meth) acrylates of polyether diols such as tetraethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth). ) Acrylates, di (meth) acrylates of polyalkyldiols such as 1,9-nonanediol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, cyclohexanediol di (meth) acrylate, and the like. Examples of the monofunctional reactive monomer include 2-hydroxyethyl (meth) acrylate, phenoxyethyloxyethyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, acryloylmorpholine, and N-vinyl. And formamide.
本発明の活性エネルギー線硬化性樹脂組成物は、プラスチック表面に塗布後、活性エネルギー線を照射することにより硬化する。活性エネルギー線としては、電子線、紫外線、可視光線などがある。紫外線、可視光線で硬化させる場合には、光重合開始剤が当該組成物に配合されるが、当該光重合開始剤としては格別の限定はなく各種公知のものを使用できる。具体的には、ベンゾイル安息香酸メチル、ベンゾイン、ベンジルジメチルケタール、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニル−１−プロパノン、２−メチル−１−[４−（メチルチオ）フェニル]−２−モルホリノ−１−プロパノン、１−ヒドロキシシクロヘキシルフェニルケトン、２,４−ジエチルチオキサントン、２,４,６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２,４,６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、カンファーキノン、アントラセン、ベンジル、フェニルメチルグリオキシレートなどが挙げられる。これらの光重合開始剤は、それぞれ単独または組み合わせて使用することができる。 The active energy ray-curable resin composition of the present invention is cured by irradiating active energy rays after being applied to the plastic surface. Examples of active energy rays include electron beams, ultraviolet rays, and visible rays. In the case of curing with ultraviolet light or visible light, a photopolymerization initiator is blended in the composition, but the photopolymerization initiator is not particularly limited and various known ones can be used. Specifically, methyl benzoylbenzoate, benzoin, benzyldimethyl ketal, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholino-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2,4-diethylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide , Camphorquinone, anthracene, benzyl, phenylmethylglyoxylate and the like. These photopolymerization initiators can be used alone or in combination.
本発明の活性エネルギー線硬化性樹脂組成物の硬化速度を一層向上させるために、前記光重合開始剤と光増感剤とを併用してもよい。当該光増感剤の具体例としては、トリエタノールアミン、ジエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４,４’−ジエチルアミノベンゾフェノン、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル、安息香酸−２−ジメチルアミノエチル、ジエチルアミノエチル（メタ）アクリレート、トリブチルホスフィンなどが挙げられ、これらはそれぞれ単独でまたは組み合わせて使用できる。 In order to further improve the curing rate of the active energy ray-curable resin composition of the present invention, the photopolymerization initiator and the photosensitizer may be used in combination. Specific examples of the photosensitizer include triethanolamine, diethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophenone, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid. -2-dimethylaminoethyl, diethylaminoethyl (meth) acrylate, tributylphosphine and the like can be mentioned, and these can be used alone or in combination.
また、本発明の活性エネルギー線硬化性樹脂組成物は、前記各種成分に加えて、表面平滑剤、界面活性剤、紫外線吸収剤、無機フィラー、シランカップリング剤、コロイダルシリカ、接着性改良剤、消泡剤、湿潤剤、防錆剤あるいは貯蔵安定剤などの添加剤を適宜配合することができる。 Moreover, the active energy ray-curable resin composition of the present invention includes, in addition to the above-mentioned various components, a surface smoothing agent, a surfactant, an ultraviolet absorber, an inorganic filler, a silane coupling agent, colloidal silica, an adhesion improver, Additives such as antifoaming agents, wetting agents, rust inhibitors and storage stabilizers can be appropriately blended.
本発明の活性エネルギー線硬化性樹脂組成物は、各種の基材（プラスチック成形品フィルム、シートなど）の表面に塗布され、重合硬化される。当該塗布方法としては、刷毛塗り塗工、流延塗工、ローラーコート塗工、バーコーター塗工、メイヤーバー塗工、噴霧塗工、エアーナイフ塗工、ディッピング塗工、グラビア塗工、リバースグラビア塗工、オフセット印刷、フレキソ印刷、スクリーン印刷等の公知各種の方法を格別限定なく採用できる。当該硬化性樹脂組成物の塗布量としては、格別限定されず、用途に応じて適宜に決定できるが、通常は硬化膜厚が０．５〜１０μｍ程度になる量とされる。膜厚が、０.５μｍ未満の場合は、帯電防止性、耐摩耗性が低下する傾向があり、また膜厚が１０μｍを超える場合には、硬化皮膜にクラック等が発生する傾向がある。 The active energy ray-curable resin composition of the present invention is applied to the surface of various base materials (plastic molded product films, sheets, etc.) and polymerized and cured. The application methods include brush coating, cast coating, roller coating, bar coater coating, Mayer bar coating, spray coating, air knife coating, dipping coating, gravure coating, and reverse gravure coating. Various known methods such as coating, offset printing, flexographic printing, and screen printing can be employed without any particular limitation. The coating amount of the curable resin composition is not particularly limited, and can be appropriately determined according to the use, but is usually an amount such that the cured film thickness is about 0.5 to 10 μm. When the film thickness is less than 0.5 μm, the antistatic property and wear resistance tend to be reduced, and when the film thickness exceeds 10 μm, cracks and the like tend to occur in the cured film.
紫外線により硬化させる場合、光源としてキセノンランプ、高圧水銀灯、メタルハライドランプを有する紫外線照射装置が使用され、必要に応じて光量、光源の配置などが調整されるが、高圧水銀灯を使用する場合、８０〜１２０Ｗ/ｃｍの光量を有したランプ１灯に対して搬送速度５〜６０ｍ／分で硬化させるのが好ましい。一方、電子線により硬化させる場合、１００〜５００ｅＶのエネルギーを有する電子線加速装置の使用が好ましい。 In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp as a light source is used, and the amount of light and the arrangement of the light source are adjusted as necessary. It is preferable to cure at a conveyance speed of 5 to 60 m / min with respect to one lamp having a light quantity of 120 W / cm. On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having energy of 100 to 500 eV.
本発明の活性エネルギー線硬化性樹脂組成物が適用できるプラスチック基材の種類や形状に関しては、格別限定なく、公知各種のものが使用できる。これらの具体例としては、ポリオレフィン系樹脂、ポリスチレン系樹脂、アセタール樹脂、アクリル樹脂、飽和ポリエステル、ポリカーボネート、塩化ビニル系樹脂、フッ素樹脂、液晶ポリエステル、ポリアリレート、ポリスルホン、ポリフェニレンエーテルなどの熱可塑性樹脂や、アルキド樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、ジアリルテレフタレート樹脂、ポリイミド、シリコーン樹脂などの熱硬化性樹脂などがある。またプラスチック基材の形状としては、例えば、成形品、フィルム、シートなどが挙げられる。 With respect to the type and shape of the plastic substrate to which the active energy ray-curable resin composition of the present invention can be applied, various known materials can be used without any particular limitation. Specific examples of these include thermoplastic resins such as polyolefin resins, polystyrene resins, acetal resins, acrylic resins, saturated polyesters, polycarbonates, vinyl chloride resins, fluororesins, liquid crystal polyesters, polyarylate, polysulfone, and polyphenylene ether. And thermosetting resins such as alkyd resin, unsaturated polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, urea resin, diallyl terephthalate resin, polyimide, and silicone resin. Examples of the shape of the plastic substrate include a molded product, a film, and a sheet.
以下に、実施例をあげて本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお以下「部」及び「％」は、特記しない限りいずれも質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Hereinafter, “parts” and “%” are based on mass unless otherwise specified.
（紫外線硬化性樹脂組成物の調合）
（Ａ）成分として、ビームセット５７５Ｂ（荒川化学工業（株）製、多官能ウレタンアクリレート）、（Ｂ）成分として、グラノール４４０（共栄社化学（株）製）、（Ｃ）成分としてリチウムビス（トリフルオロメタンスルホニル）イミド（森田化学工業（株）製）および光重合開始剤としてイルガキュアー１８４（チバスペシャリティケミカルズ社製）を使用し、表１に示したとおり配合し、当該配合物をそれぞれメチルエチルケトンにて５０％濃度に希釈することにより、紫外線硬化性樹脂組成物を得た。
(Preparation of UV curable resin composition)
As component (A), beam set 575B (manufactured by Arakawa Chemical Industries, Ltd., polyfunctional urethane acrylate), as component (B), Granol 440 (manufactured by Kyoeisha Chemical Co., Ltd.), as component (C), lithium bis (trifluoro) Lomethanesulfonyl) imide (manufactured by Morita Chemical Co., Ltd.) and Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator were blended as shown in Table 1, and the blends were each methylethylketone. By diluting to a concentration of 50%, an ultraviolet curable resin composition was obtained.
（塗膜の作成方法）
上記調合で得られた各種組成物を、それぞれバーコーター＃６にて７５ミクロンのポリエステルフィルム（パナック（株）製、商品名「ルミラー７５−Ｔ６０」）上に塗布し、７０℃、３０秒の条件下乾燥させた。これに高圧水銀灯にて紫外線を照射して（８０Ｗ／ｃｍ×１０ｃｍ（Ｈ）×１灯×１０ｍ／分×３パス）硬化させることにより、硬化塗膜層を有するフィルムを作成した。これらのフィルムを用いて、以下の各種試験を行った。得られた評価結果を表２に示す。
(Method for creating coating film)
Each composition obtained by the above preparation was applied on a 75 micron polyester film (manufactured by Panac Co., Ltd., trade name “Lumirror 75-T60”) with a bar coater # 6, at 70 ° C. for 30 seconds. Dry under conditions. A film having a cured coating layer was prepared by irradiating this with ultraviolet light with a high-pressure mercury lamp (80 W / cm × 10 cm (H) × 1 lamp × 10 m / min × 3 passes) and curing. The following various tests were conducted using these films. The obtained evaluation results are shown in Table 2.
（塗膜の性能評価）
表面抵抗率：リング電極（東亜電波工業（株）製、ＵＲＴＲＡ ＭＥＧＯＨＭＭＥＴＥＲ ＳＭ−８２１０、ＳＭＥ−８３１１）を用いて、ＪＩＳ Ｋ ６９１１に準じ、印加電圧５００ボルトで測定した。
耐摩耗性：スチールウール（日本スチールウール（株）製、ボンスター＃００）に３００ｇ／ｃｍ２の荷重を掛け、フィルム表面を５０回往復させ、傷が付くかどうかを目視観察し、次の評価基準とした。
○：外観変化無し。×：傷がある。
鉛筆硬度：ＪＩＳ Ｋ ５４００に準じ、鉛筆引っかき試験機を用いて、上記塗工フィルムの鉛筆硬度を測定した。
上記塗工フィルムの透明性は目視観察し、次の評価基準とした。
○：外観変化無し。×：白化。
(Evaluation of coating film performance)
Surface resistivity: Measured at an applied voltage of 500 volts according to JIS K 6911 using a ring electrode (manufactured by Toa Denpa Kogyo Co., Ltd., URTRA MEGOHMMETER SM-8210, SME-883).
Abrasion resistance: Steel wool (made by Nippon Steel Wool Co., Ltd., Bonstar # 00) was subjected to a load of 300 g / cm 2 , and the film surface was reciprocated 50 times. Standard.
○: No change in appearance. X: There are scratches.
Pencil hardness: The pencil hardness of the coated film was measured using a pencil scratch tester in accordance with JIS K 5400.
The transparency of the coated film was visually observed and used as the next evaluation standard.
○: No change in appearance. X: Whitening.
Claims (5)
The compounding quantity of the said (C) component is 0.1-30 mass parts per 100 mass parts of active energy ray-curable resin compositions, The active energy ray-curable resin composition in any one of Claims 1-4 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003345126A JP4022821B2 (en) | 2003-10-03 | 2003-10-03 | Active energy ray-curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003345126A JP4022821B2 (en) | 2003-10-03 | 2003-10-03 | Active energy ray-curable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005112885A true JP2005112885A (en) | 2005-04-28 |
| JP4022821B2 JP4022821B2 (en) | 2007-12-19 |
Family
ID=34538491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003345126A Expired - Lifetime JP4022821B2 (en) | 2003-10-03 | 2003-10-03 | Active energy ray-curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4022821B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006070062A (en) * | 2004-08-31 | 2006-03-16 | Kimoto & Co Ltd | Antistatic hard coat coating, antistatic hard coat film using the same and molding |
| JP2006111868A (en) * | 2004-09-16 | 2006-04-27 | Dainippon Ink & Chem Inc | Active energy ray-curing resin composition and synthetic resin molded product |
| JP2007070395A (en) * | 2005-09-05 | 2007-03-22 | Denki Kagaku Kogyo Kk | Resin composition for antistatic hard coat and its use |
| JP2007070456A (en) * | 2005-09-07 | 2007-03-22 | Aica Kogyo Co Ltd | Antistatic hard coating agent and hard coat film for touch panel |
-
2003
- 2003-10-03 JP JP2003345126A patent/JP4022821B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006070062A (en) * | 2004-08-31 | 2006-03-16 | Kimoto & Co Ltd | Antistatic hard coat coating, antistatic hard coat film using the same and molding |
| JP2006111868A (en) * | 2004-09-16 | 2006-04-27 | Dainippon Ink & Chem Inc | Active energy ray-curing resin composition and synthetic resin molded product |
| JP2007070395A (en) * | 2005-09-05 | 2007-03-22 | Denki Kagaku Kogyo Kk | Resin composition for antistatic hard coat and its use |
| JP2007070456A (en) * | 2005-09-07 | 2007-03-22 | Aica Kogyo Co Ltd | Antistatic hard coating agent and hard coat film for touch panel |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4022821B2 (en) | 2007-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2657293B1 (en) | Water-absorbable resin composition and laminate produced using same | |
| JP2007016145A (en) | Active energy ray-curable resin composition | |
| JP5092907B2 (en) | Active energy ray curable resin composition, active energy ray curable hard coating agent, cured film using these, and article having cured film | |
| TW201816016A (en) | Antifog coating composition | |
| KR20180108456A (en) | Active-energy-ray curable hard coating agent, curable coating film, laminated film | |
| JP2009287017A (en) | Active energy ray-curable resin composition, cured product and article | |
| JP5142075B2 (en) | Active energy ray curable resin, active energy ray curable resin composition, and article having a hard coat layer obtained using the same | |
| JP4022821B2 (en) | Active energy ray-curable resin composition | |
| JP5093868B2 (en) | Composition for ultraviolet curable coating and method for producing laminate using the same | |
| JP3066159B2 (en) | Composition for forming hard coat | |
| JP2006326426A (en) | Method for forming antistatic coating film | |
| JP5407102B2 (en) | Active energy ray-curable resin composition for protecting cyclic olefin resin substrate surface | |
| JP6701690B2 (en) | Coating agent composition for coating glass substrate | |
| JPS6328095B2 (en) | ||
| KR100383086B1 (en) | UV-curable coating composition with excellent antistatic properties and adhesion to the conductor | |
| JPH09268260A (en) | Active energy ray-curable coating material for plastic and plastic molded product whose surface is treated with the coating material | |
| KR100290538B1 (en) | UV curing anti-static hard coating | |
| JP2022153309A (en) | Active energy ray curable composition and its cured material | |
| JP3690191B2 (en) | Products with a hard coat layer | |
| JP2020164663A (en) | Coating liquid for forming transparent film | |
| JP2006070062A (en) | Antistatic hard coat coating, antistatic hard coat film using the same and molding | |
| JP5014625B2 (en) | Antistatic coating composition and film obtained by curing the same | |
| JP2014181320A (en) | Active energy ray-curable composition and cured product | |
| JP2010001399A (en) | Antistatic coating composition and film obtained by curing the same | |
| JP5014634B2 (en) | Antistatic coating agent composition and film obtained by curing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050606 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070621 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070625 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070816 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070906 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070919 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4022821 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101012 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101012 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101012 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111012 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111012 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121012 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121012 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121012 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131012 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |