JP2017179368A - Active energy ray curable composition and coating film - Google Patents
Active energy ray curable composition and coating film Download PDFInfo
- Publication number
- JP2017179368A JP2017179368A JP2017062960A JP2017062960A JP2017179368A JP 2017179368 A JP2017179368 A JP 2017179368A JP 2017062960 A JP2017062960 A JP 2017062960A JP 2017062960 A JP2017062960 A JP 2017062960A JP 2017179368 A JP2017179368 A JP 2017179368A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- active energy
- solid content
- energy ray
- component
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 239000011248 coating agent Substances 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 title claims description 20
- 239000007787 solid Substances 0.000 claims abstract description 99
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 75
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 26
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 16
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 16
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- -1 cyclic olefin Chemical class 0.000 abstract description 18
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 239000010408 film Substances 0.000 description 49
- 238000006243 chemical reaction Methods 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 15
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 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 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000193 polymethacrylate Polymers 0.000 description 4
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 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 3
- 238000005259 measurement Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-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
- 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 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
- 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
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-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
- 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- BBKPDHOKNRMWQN-UHFFFAOYSA-N nonane-1,4-diol Chemical compound CCCCCC(O)CCCO BBKPDHOKNRMWQN-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、活性エネルギー線硬化型組成物及びコーティングフィルムに関する。 The present invention relates to an active energy ray-curable composition and a coating film.
従来、液晶表示装置に用いられる偏光板は、ポリビニルアルコールフィルムにヨウ素等を吸着させ延伸等により配向させた偏光子の両面に保護フィルムとしてトリアセチルセルロースフィルム（ＴＡＣフィルム）を貼りあわせ、さらにその表面には、透明な光硬化型樹脂組成物を塗布、硬化させて高硬度の被膜（ハードコート層）が形成され、傷つき等から保護されている。このような硬化被膜を形成させる材料として、多官能（メタ）アクリレート等を用いた活性エネルギー線硬化型の樹脂組成物が知られている（特許文献１）。 Conventionally, a polarizing plate used in a liquid crystal display device is obtained by bonding a triacetyl cellulose film (TAC film) as a protective film on both surfaces of a polarizer obtained by adsorbing iodine or the like on a polyvinyl alcohol film and orienting the film by stretching or the like. A transparent photocurable resin composition is applied and cured to form a high-hardness film (hard coat layer), which is protected from scratches and the like. As a material for forming such a cured film, an active energy ray-curable resin composition using polyfunctional (meth) acrylate or the like is known (Patent Document 1).
近年、液晶装置の大型化や高品質化及びモバイル用途の拡大からより厳しい使用環境（例えば、高温、高湿条件等）に耐えるものが求められ、ＴＡＣフィルムは特性面において限界があることが明らかになった。そのような中で、保護フィルムの材質について種々の検討がなされ、ＴＡＣフィルムから環状オレフィン樹脂系フィルムへの代替が有望視されている状況にある。環状オレフィン樹脂系フィルムは透明性、低複屈折、寸法安定性等に優れ、光学用フィルムとして必要な性能を備えている。更に、低透湿性を有することも大きな特徴であり、この点においてＴＡＣフィルムを代替する大きな要因となっている。しかしながら、環状オレフィン樹脂系フィルムは、フィルム表面に高い密着性を有するハードコート層を形成させることが難しいという問題がある。 In recent years, liquid crystal devices are required to withstand more severe use environments (for example, high temperature, high humidity conditions, etc.) due to the increase in size, quality, and expansion of mobile applications, and it is clear that TAC films have limitations in terms of characteristics. Became. Under such circumstances, various studies have been made on the material of the protective film, and there is a promising alternative to the cyclic olefin resin film from the TAC film. The cyclic olefin resin-based film is excellent in transparency, low birefringence, dimensional stability, and the like, and has necessary performance as an optical film. Furthermore, having a low moisture permeability is also a great feature, and in this respect, it is a major factor to replace the TAC film. However, the cyclic olefin resin film has a problem that it is difficult to form a hard coat layer having high adhesion on the film surface.
従来は環状オレフィン樹脂系フィルムに対してはプライマー層の塗布や電気的処理（コロナ放電処理、大気圧プラズマ処理）を行うことにより、基材とハードコート層との密着を高めていた（特許文献２）。 Conventionally, the adhesion between the base material and the hard coat layer has been enhanced by applying a primer layer and applying electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment) to the cyclic olefin resin film (Patent Literature). 2).
しかし、前述の方法では、塗布フィルムを生産する際に基材と密着性とを高めるための処理工程が必要となり、コスト高に繋がるという問題があった。また、電気的処理は処理面の経時変化が生じるため処理後に速やかにハードコート層を塗布しなければならないという制約もあった。 However, the above-described method has a problem in that it requires a processing step for increasing the base material and adhesion when producing a coated film, leading to high costs. Moreover, since electrical treatment causes changes in the treated surface over time, there is a restriction that a hard coat layer must be applied immediately after the treatment.
本発明は、良好な塗工性を有し、特に環状オレフィン基材に対する高い密着性及び耐擦傷性を有する活性エネルギー線硬化型組成物及びこれを用いたコーティングフィルムを提供することを目的とする。 An object of the present invention is to provide an active energy ray-curable composition having good coating properties, particularly having high adhesion to a cyclic olefin substrate and scratch resistance, and a coating film using the same. .
本発明者は、前記課題を解決すべく鋭意検討したところ、特定の構造を導入した反応物を用いることにより、前記課題を解決することができることを見出し、本発明を完成させた。 The present inventor has intensively studied to solve the above problems, and has found that the above problems can be solved by using a reactant into which a specific structure is introduced, and has completed the present invention.
すなわち、本発明により、以下の項目が提供される。 That is, the following items are provided by the present invention.
（項目１）
全固形分をトルエンにて重量％で固形分８０％に希釈した際の２５℃でのＥ型粘度が３００〜１００００ｍＰａ・ｓであり、
全有機物固形分に対して活性エネルギー線硬化型オリゴマー（Ａ）を１５〜８０重量％含有し、
該（Ａ）成分は、（１）（メタ）アクリロイル基、（２）ポリペンタエリスリトール骨格並びに（３）イソシアヌレート基及び／又はビウレット基を有し、重量平均分子量（Ｍｗ）が３０００〜１０００００、ウレタン結合当量が３５０〜２０００ｇ／ｅｑ、（メタ）アクリロイル当量が１２０〜２５０ｇ／ｅｑである、活性エネルギー線硬化型組成物。
（項目２）
環状オレフィン樹脂フィルム用である、上記項目に記載の活性エネルギー線硬化型組成物。
（項目３）
光重合開始剤（Ｂ）を含有する、上記項目のいずれか１項に記載の活性エネルギー線硬化型組成物。
（項目４）
基材の少なくとも片面に上記項目のいずれか１項に記載の活性エネルギー線硬化型組成物の硬化被膜が形成された、コーティングフィルム。
（項目５）
前記基材が環状オレフィン樹脂である、上記項目に記載のコーティングフィルム。
（項目６）
前記基材が易接着処理を行っていない、上記項目のいずれか１項に記載のコーティングフィルム。
(Item 1)
The E-type viscosity at 25 ° C. when the total solid content is diluted with toluene to 80% solid content by weight is 300 to 10,000 mPa · s,
Containing 15 to 80% by weight of active energy ray-curable oligomer (A) based on the total organic solid content,
The component (A) has (1) (meth) acryloyl group, (2) polypentaerythritol skeleton, and (3) isocyanurate group and / or biuret group, and has a weight average molecular weight (Mw) of 3000 to 100,000. An active energy ray-curable composition having a urethane bond equivalent of 350 to 2000 g / eq and a (meth) acryloyl equivalent of 120 to 250 g / eq.
(Item 2)
The active energy ray-curable composition according to the above item, which is for a cyclic olefin resin film.
(Item 3)
The active energy ray hardening-type composition of any one of the said item containing a photoinitiator (B).
(Item 4)
A coated film in which a cured film of the active energy ray-curable composition according to any one of the above items is formed on at least one surface of a substrate.
(Item 5)
The coating film as described above, wherein the substrate is a cyclic olefin resin.
(Item 6)
The coating film according to any one of the above items, wherein the substrate is not subjected to an easy adhesion treatment.
本発明によれば、特に環状オレフィンに対する密着性が高く、耐擦傷性にも優れるため、特に液晶表示装置等の偏光板に用いられるＴＡＣフィルムに対する代替品としての環状オレフィン樹脂系フィルムに対するハードコーティング剤として好適である。 According to the present invention, a hard coating agent for a cyclic olefin resin film as an alternative to a TAC film particularly used for a polarizing plate of a liquid crystal display device or the like because of its high adhesion to a cyclic olefin and excellent scratch resistance. It is suitable as.
１つの局面において、本発明の活性エネルギー線硬化型組成物は、全固形分をトルエンにて重量％で固形分８０％に希釈した際の２５℃でのＥ型粘度が３００〜１００００ｍＰａ・ｓであり、全有機物固形分に対して活性エネルギー線硬化型オリゴマー（Ａ）（以下、「（Ａ）成分」ともいう。）を１５〜８０重量％含有し、
該（Ａ）成分は、（１）（メタ）アクリロイル基、（２）ポリペンタエリスリトール骨格並びに（３）イソシアヌレート基及び／又はビウレット基を有し、重量平均分子量（Ｍｗ）が３０００〜１０００００、ウレタン結合当量が３５０〜２０００ｇ／ｅｑ、（メタ）アクリロイル当量が１２０〜２５０ｇ／ｅｑである。上記組成物は環状オレフィン樹脂フィルム用として用いることができる。また活性エネルギー線の例としては、紫外線、電子線、放射線等が挙げられる。なお、本開示において、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルの両者を包括的に含むことを意味し、同様に「（メタ）アクリレート」は、アクリレート及びメタクリレートの両者を包括的に含むことを意味する。
In one aspect, the active energy ray-curable composition of the present invention has an E-type viscosity of 300 to 10,000 mPa · s at 25 ° C. when the total solid content is diluted with toluene to 80% solid content by weight. Yes, containing 15 to 80% by weight of active energy ray-curable oligomer (A) (hereinafter also referred to as “component (A)”) based on the total organic solid content,
The component (A) has (1) (meth) acryloyl group, (2) polypentaerythritol skeleton, and (3) isocyanurate group and / or biuret group, and has a weight average molecular weight (Mw) of 3000 to 100,000. The urethane bond equivalent is 350 to 2000 g / eq, and the (meth) acryloyl equivalent is 120 to 250 g / eq. The composition can be used for a cyclic olefin resin film. Examples of active energy rays include ultraviolet rays, electron beams, and radiation. In the present disclosure, “(meth) acryloyl” means comprehensively including both acryloyl and methacryloyl, and similarly, “(meth) acrylate” comprehensively includes both acrylate and methacrylate. Means.
（Ａ）成分に含有する成分として、ポリペンタエリスリトール骨格並びにイソシアヌレート基及び／又はビウレット基を有することにより、上記（Ａ）成分を含む活性エネルギー線硬化型組成物から得られる硬化物（コーティングフィルム）の密着性及び耐擦傷性が十分なものとなる。 As a component contained in the component (A), a cured product (coating film) obtained from the active energy ray-curable composition containing the component (A) by having a polypentaerythritol skeleton and an isocyanurate group and / or a biuret group. ) And the scratch resistance are sufficient.
上記（Ａ）成分としては、例えば、ビウレット構造を有するイソシアネート化合物とポリペンタエリスリトールポリ（メタ）アクリレートとの反応物、イソシアヌレート構造を有するイソシアネート化合物とジペンタエリスリトールポリ（メタ）アクリレートとの反応物等が挙げられる。具体的には、例えばヘキサメチレンジイソシアネートのビウレット変性体とジペンタエリスリトールヘキサアクリレートとの反応物、ヘキサメチレンジイソシアネートのイソシアヌレート変性体とジペンタエリスリトールヘキサアクリレートとの反応物が挙げられる。 Examples of the component (A) include a reaction product of an isocyanate compound having a biuret structure and polypentaerythritol poly (meth) acrylate, and a reaction product of an isocyanate compound having an isocyanurate structure and dipentaerythritol poly (meth) acrylate. Etc. Specifically, for example, a reaction product of a biuret-modified product of hexamethylene diisocyanate and dipentaerythritol hexaacrylate, a reaction product of an isocyanurate-modified product of hexamethylene diisocyanate and dipentaerythritol hexaacrylate, and the like.
上記ビウレット構造を有するイソシアネート化合物としては、例えば１，６−ヘキサメチレンジイソシアネート等の脂肪族イソシアネートのビウレット変性体、水添キシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネートのビウレット変性体、キシレンジイソシアネート等の芳香族イソシアネートのビウレット変性体等が挙げられる。 Examples of the isocyanate compound having a biuret structure include biuret-modified products of aliphatic isocyanates such as 1,6-hexamethylene diisocyanate, biuret-modified products of alicyclic isocyanates such as hydrogenated xylene diisocyanate and isophorone diisocyanate, and xylene diisocyanate. And biuret-modified products of aromatic isocyanate.
上記イソシアヌレート構造を有するイソシアネート化合物としては、例えば、１，６−ヘキサメチレンジイソシアネート等の脂肪族イソシアネートのイソシアヌレート変性体、水添キシレンジイソシアネート、イソホロンジイソシアネート等の脂環族イソシアネートのイソシアヌレート変性体、キシレンジイソシアネート等の芳香族イソシアネートのイソシアヌレート変性体等が挙げられる。 Examples of the isocyanate compound having an isocyanurate structure include, for example, isocyanurate-modified products of aliphatic isocyanates such as 1,6-hexamethylene diisocyanate, isocyanurate-modified products of alicyclic isocyanates such as hydrogenated xylene diisocyanate and isophorone diisocyanate, Examples include isocyanurate-modified products of aromatic isocyanates such as xylene diisocyanate.
上記ポリペンタエリスリトール骨格を有する化合物としては、例えば、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタアクリレートのエチレンオキサイド変性物、ジペンタエリスリトールペンタアクリレートのカプロラクトン変性物、ポリペンタエリスリトールポリアクリレート、ポリペンタエリスリトールポリアクリレートのエチレンオキサイド変性物、ポリペンタエリスリトールポリアクリレートのカプロラクトン変性物及びこれらの２種以上の混合物が挙げられる。 Examples of the compound having a polypentaerythritol skeleton include dipentaerythritol pentaacrylate, ethylene oxide-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol pentaacrylate, polypentaerythritol polyacrylate, polypentaerythritol poly An ethylene oxide modified product of acrylate, a caprolactone modified product of polypentaerythritol polyacrylate, and a mixture of two or more of these.
上記反応物の製造方法としては、例えば、上記イソシアネート化合物とジペンタエリスリトール骨格を有する化合物とをトリエチレンジアミン、１，８−ジアザビシクロ−［５，４，０］−ウンデセン−７、オクチル酸スズ、ジオクチル酸鉛等のウレタン化触媒の存在下、４０〜９０℃の温度範囲で反応させる方法等が挙げられる。 Examples of the method for producing the reaction product include triethylenediamine, 1,8-diazabicyclo- [5,4,0] -undecene-7, tin octylate, dioctyl and the above isocyanate compound and a compound having a dipentaerythritol skeleton. Examples include a method of reacting in the temperature range of 40 to 90 ° C. in the presence of a urethanization catalyst such as lead acid.
上記（Ａ）成分を含有する活性エネルギー線硬化型組成物の全固形分をトルエンにて重量％で固形分８０％に希釈した際の２５℃でのＥ型粘度の上限の例としては、１００００、９０００、８０００、７０００、６０００、５０００、４０００、３０００、２０００、１０００、９００、８００、７００、６００、５００、４００ｍＰａ・ｓ等が挙げられ、下限の例としては、９０００、８０００、７０００、６０００、５０００、４０００、３０００、２０００、１０００、９００、８００、７００、６００、５００、４００、３００ｍＰａ・ｓ等が挙げられる。上記Ｅ型粘度の範囲は適宜（例えば上記上限及び下限の値から選択して）設定することができる。１つの実施形態において、塗工性の観点から、上記Ｅ型粘度の範囲は３００〜１００００ｍＰａ・ｓであり、好ましくは４５０〜２０００ｍＰａ・ｓである。上記Ｅ型粘度（ｍＰａ・ｓ）は、上記（Ａ）成分を含有する活性エネルギー線硬化型組成物をトルエンにて重量％で固形分８０％へ希釈した溶液を２５℃でＥ型粘度計（東機産業社製 ＴＶ−２２ ３°コーン）にて、約０．４ｍＬを測定用試料とし、回転速度０．５〜１００ｒｐｍ、５分間回転の条件で測定することができる。本発明の活性エネルギー線硬化型組成物は、（Ａ）成分を製造する工程で残存モノマーや後述する重合開始剤等のその他の成分も含まれる。 As an example of the upper limit of the E-type viscosity at 25 ° C. when the total solid content of the active energy ray-curable composition containing the component (A) is diluted to 80% by weight with toluene, 10000 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400 mPa · s, etc., and examples of the lower limit include 9000, 8000, 7000, 6000. 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400, 300 mPa · s and the like. The range of the E-type viscosity can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, from the viewpoint of coatability, the range of the E-type viscosity is 300 to 10,000 mPa · s, preferably 450 to 2000 mPa · s. The E-type viscosity (mPa · s) is a solution obtained by diluting the active energy ray-curable composition containing the component (A) with toluene to 80% solid content by weight at 25 ° C. at 25 ° C. ( About 0.4 mL can be used as a measurement sample with a TV-22 3 ° cone manufactured by Toki Sangyo Co., Ltd., and measurement can be performed under conditions of a rotation speed of 0.5 to 100 rpm and a rotation for 5 minutes. The active energy ray-curable composition of the present invention includes other components such as a residual monomer and a polymerization initiator described later in the step of producing the component (A).
上記（Ａ）成分の重量平均分子量（Ｍｗ）（ゲルパーメーションクロマトグラフィーによるポリスチレン換算値）の上限の例としては、１０００００、９００００、８００００、７００００、６００００、５００００、４６０００、４００００、３００００、２００００、１５６００、１３５００、１１０００、１０５００、１００００、８５００、８０００、５０００等が挙げられ、下限の例としては、９００００、８００００、７００００、６００００、５００００、４６０００、４００００、３００００、２００００、１５６００、１３５００、１１０００、１０５００、１００００、８５００、８０００、５０００、３０００等が挙げられる。重量平均分子量（Ｍｗ）の範囲は適宜（例えば上記上限及び下限の値から選択して）設定することができる。１つの実施形態において、重量平均分子量（Ｍｗ）の範囲は基材への密着性、塗料安定性、印刷適性の観点から、３０００〜１０００００である。好ましくは、５０００〜８００００であり、より好ましくは、８０００〜５００００である。 Examples of the upper limit of the weight average molecular weight (Mw) of the component (A) (polystyrene conversion value by gel permeation chromatography) are 100,000, 90,000, 80,000, 70,000, 60000, 50000, 46000, 40000, 30000, 20000, 15600, 13500, 11000, 10500, 10000, 8500, 8000, 5000 and the like. Examples of the lower limit include 90000, 80000, 70000, 60000, 50000, 46000, 40000, 30000, 20000, 15600, 13500, 11000, 10500, 10000, 8500, 8000, 5000, 3000 etc. are mentioned. The range of the weight average molecular weight (Mw) can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, the range of the weight average molecular weight (Mw) is 3000 to 100,000 from the viewpoints of adhesion to a substrate, paint stability, and printability. Preferably, it is 5000-80000, More preferably, it is 8000-50000.
上記（Ａ）成分のウレタン結合当量の上限の例としては、１５００、１４００、１３００、１２００、１１００、１０００、９７６、９００、８００、７５０、７４８、７３５、７２５、７００、６１２、６００、５００、４００ｇ／ｅｑ等が挙げられ、下限の例としては、１４００、１３００、１２００、１１００、１０００、９７６、９００、８００、７５０、７４８、７３５、７２５、７００、６１２、６００、５００、４００ｇ／ｅｑ等が挙げられる。上記ウレタン結合当量の範囲は適宜（例えば上記上限及び下限の値から選択して）設定することができる。１つの実施形態において、上記ウレタン結合当量の範囲は耐擦傷性、密着性の観点から、３５０〜２０００ｇ／ｅｑであり、好ましくは、３５０〜１５００ｇ／ｅｑ、より好ましくは６００〜１０００ｇ／ｅｑである。ウレタン結合当量とは、反応原料の仕込み量から算出される値であり、具体的には全原料の総重量を成分（Ａ）の全原料中に含まれる水酸基と反応し得るイソシアネート基のモル数で除した値である。 Examples of the upper limit of the urethane bond equivalent of the component (A) are 1500, 1400, 1300, 1200, 1100, 1000, 976, 900, 800, 750, 748, 735, 725, 700, 612, 600, 500, 400g / eq etc. are mentioned, As an example of a lower limit, 1400, 1300, 1200, 1100, 1000, 976, 900, 800, 750, 748, 735, 725, 700, 612, 600, 500, 400 g / eq etc. Is mentioned. The range of the urethane bond equivalent can be appropriately set (for example, selected from the above upper limit and lower limit values). In one embodiment, the range of the urethane bond equivalent is 350 to 2000 g / eq, preferably 350 to 1500 g / eq, more preferably 600 to 1000 g / eq, from the viewpoint of scratch resistance and adhesion. . The urethane bond equivalent is a value calculated from the charged amount of the reaction raw material. Specifically, the total weight of all raw materials is the number of moles of isocyanate groups that can react with the hydroxyl groups contained in all the raw materials of component (A). The value divided by.
上記（Ａ）成分の（メタ）アクリロイル当量の上限の例としては、２５０、２４０、２３０、２２０、２１０、２００、１９６、１９０、１８０、１７０、１６０、１５６、１５０、１４７、１４５、１４０、１３０ｇ／ｅｑ等が挙げられ、下限の例としては、２４０、２３０、２２０、２１０、２００、１９６、１９０、１８０、１７０、１６０、１５６、１５０、１４７、１４５、１４０、１３０ｇ／ｅｑ等が挙げられる。上記（メタ）アクリロイル当量の範囲は適宜（例えば上記上限及び下限の値から選択して）設定することができる。１つの実施形態において、上記（メタ）アクリロイル当量の範囲は工業的な合成、耐擦傷性の観点から、１２０〜２５０ｇ／ｅｑが好ましく、１２０〜２００ｇ／ｅｑがより好ましい。（メタ）アクリロイル当量とは、反応原料の仕込み量から算出される値であり、具体的には全原料の総重量を（Ａ）成分の全原料中に含まれる（メタ）アクリロイル基のモル数で除した値である。 Examples of the upper limit of the (meth) acryloyl equivalent of the component (A) are 250, 240, 230, 220, 210, 200, 196, 190, 180, 170, 160, 156, 150, 147, 145, 140, Examples of the lower limit include 240, 230, 220, 210, 200, 196, 190, 180, 170, 160, 156, 150, 147, 145, 140, 130 g / eq, and the like. It is done. The range of the (meth) acryloyl equivalent can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, the range of the (meth) acryloyl equivalent is preferably 120 to 250 g / eq, more preferably 120 to 200 g / eq, from the viewpoint of industrial synthesis and scratch resistance. The (meth) acryloyl equivalent is a value calculated from the charged amount of reaction raw materials, and specifically, the total weight of all raw materials is the number of moles of (meth) acryloyl groups contained in all raw materials of component (A). The value divided by.
イソシアネート基由来の官能基を有する活性エネルギー線硬化型オリゴマー１００重量％に対する前記（Ａ）成分の割合が５０重量％以上であることが好ましい。これにより、良好な密着性を発現することができる。より好ましくは７５〜１００重量％である。またイソシアヌレート基及びビウレット基の両方を含む場合、その官能基の各割合は任意でよい。 The ratio of the component (A) to 100% by weight of the active energy ray-curable oligomer having a functional group derived from an isocyanate group is preferably 50% by weight or more. Thereby, favorable adhesiveness can be expressed. More preferably, it is 75 to 100% by weight. Moreover, when both an isocyanurate group and a biuret group are included, each ratio of the functional group may be arbitrary.
本発明の活性エネルギー線硬化型組成物に含まれる、全有機物固形分に対する（Ａ）成分の含有率の上限の例としては、８０、７０、６０、５８、５０、４９、４３、４０、３９、３４、３０、２０、１７重量％等が挙げられ、下限の例としては、７０、６０、５８、５０、４９、４３、４０、３９、３４、３０、２０、１７、１５重量％等が挙げられる。全有機物固形分に対する（Ａ）成分の含有率の範囲は適宜（例えば上記上限及び下限の値から選択して）設定することができる。１つの実施形態において、全有機物固形分に対する（Ａ）成分の含有率の範囲は基材への塗工性や密着性の観点から、上記（Ａ）成分を１５〜８０重量％、好ましくは、１５〜５０重量％を含有する。ここで「固形分」とは溶剤を除く成分を意味し、「全有機物固形分」とは、全固形分からシリカフィラー等の無機物の固形分を除いた固形分を意味する。 Examples of the upper limit of the content of component (A) with respect to the total organic solid content contained in the active energy ray-curable composition of the present invention are 80, 70, 60, 58, 50, 49, 43, 40, 39. , 34, 30, 20, 17% by weight, and examples of the lower limit include 70, 60, 58, 50, 49, 43, 40, 39, 34, 30, 20, 17, 15% by weight, etc. Can be mentioned. The range of the content of the component (A) relative to the total organic solid content can be set as appropriate (for example, selected from the above upper limit and lower limit values). In one embodiment, the range of the content ratio of the component (A) with respect to the total organic solid content is 15 to 80% by weight of the component (A) from the viewpoint of coating properties and adhesion to the substrate, preferably, Contains 15-50% by weight. Here, the “solid content” means a component excluding the solvent, and the “total organic solid content” means a solid content obtained by removing an inorganic solid content such as a silica filler from the total solid content.
基材の少なくとも片面に本発明の活性エネルギー線硬化型組成物の硬化被膜が形成されたコーティングフィルムもまた本発明の１つである。透明度が高く、低透湿性の環状オレフィン樹脂系フィルムに対して、本発明の環状オレフィン樹脂フィルム用活性エネルギー線硬化型組成物を用いることにより、耐擦傷性に優れたコーティングを基材への高い密着性を確保しつつ実施できるため、偏光板の保護フィルムに好適に用いることができる。 A coating film in which a cured film of the active energy ray-curable composition of the present invention is formed on at least one surface of the substrate is also one aspect of the present invention. By using the active energy ray-curable composition for cyclic olefin resin film of the present invention for a cyclic olefin resin film having high transparency and low moisture permeability, a coating excellent in scratch resistance can be applied to a substrate. Since it can implement, ensuring adhesiveness, it can use suitably for the protective film of a polarizing plate.
上記基材は、環状オレフィン系樹脂、トリアセチルセルロース、ポリカーボネート、ポリメチルメタクリレート、ポリスチレン、ポリエステル、メラミン樹脂、エポキシ樹脂、ＡＢＳ樹脂、ノルボルネン系樹脂、ポリイミド樹脂等が挙げられる。これらの中で環状オレフィン樹脂を基材とした場合に高い密着性を有するため好ましい。より好ましくは易接着処理を行っていない基材である。これを用いることで、生産コストの低減や製造工程の制約を除くことが出来る。 Examples of the substrate include cyclic olefin resin, triacetyl cellulose, polycarbonate, polymethyl methacrylate, polystyrene, polyester, melamine resin, epoxy resin, ABS resin, norbornene resin, and polyimide resin. Among these, when a cyclic olefin resin is used as a base material, it is preferable because it has high adhesion. More preferably, the substrate is not subjected to easy adhesion treatment. By using this, it is possible to reduce the production cost and eliminate the restrictions on the manufacturing process.
上記易接着処理としては、例えば、表面凹凸処理（サンドブラスト法、溶剤処理法）、電気的処理（コロナ放電処理、大気圧プラズマ処理）、火炎処理、電子線照射処理等が挙げられる。 Examples of the easy adhesion treatment include surface unevenness treatment (sand blast method, solvent treatment method), electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), flame treatment, electron beam irradiation treatment, and the like.
本発明の活性エネルギー線硬化型組成物は、上記（Ａ）成分に加え、本発明の効果を損なわない範囲で（Ａ）成分以外の（メタ）アクリレート成分、光増感剤、酸化防止剤、光安定剤、レベリング剤、顔料等の各種公知の添加剤及び光重合開始剤（Ｂ）（以下、「（Ｂ）成分」ともいう）等を含有させてもよい。ここで上記添加剤は、上記（Ａ）成分、（Ａ）成分以外の（メタ）アクリレート成分、（Ｂ）成分以外の剤を意味し、組成物中の含有量の例としては、組成物１００重量部に対し、１０重量部未満、１重量部未満、０．１重量部未満、０．０１重量部未満等が挙げられるが、これに限定されるものではない。 In addition to the above component (A), the active energy ray-curable composition of the present invention is a (meth) acrylate component other than the component (A), a photosensitizer, an antioxidant, Various known additives such as a light stabilizer, a leveling agent, and a pigment, and a photopolymerization initiator (B) (hereinafter, also referred to as “component (B)”) may be contained. Here, the additive means the component (A), the (meth) acrylate component other than the component (A), and the agent other than the component (B). As an example of the content in the composition, the composition 100 Less than 10 parts by weight, less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, and the like may be mentioned with respect to parts by weight, but it is not limited thereto.
上記（Ａ）成分以外の（メタ）アクリレート成分としては、特に限定されず、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、ジトリメチロールプロパンテトラ（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、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（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ポリ（メタ）アクリレート、ペンタエリスリトールポリ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートトリ（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、１，４−ノナンジオールジ（メタ）アクリレート、２−ヒドロキシエチルアクリレート、ベンジルアクリレート、トリデシル（メタ）アクリレート、ラウリル（メタ）アクリレート等が挙げられる。（Ａ）成分以外の（メタ）アクリレート成分を配合する場合、（Ａ）成分と配合する（Ａ）成分以外の（メタ）アクリレート成分との重量比（（Ａ）成分/（Ａ）成分以外の（メタ）アクリレート成分）、０．７〜９等が挙げられるが、この値に限定されるものではない。 The (meth) acrylate component other than the component (A) is not particularly limited. For example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, trimethylolpropane tri (Meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Poly (meth) acrylate, pentaerythritol poly (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) Examples include acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-nonanediol di (meth) acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, tridecyl (meth) acrylate, and lauryl (meth) acrylate. . (A) When mix | blending (meth) acrylate components other than component, (A) component and (meth) acrylate components other than (A) component to mix | blend (weight ratio other than (A) component / (A) component) (Meth) acrylate component), 0.7 to 9 and the like, but are not limited to this value.
上記（Ｂ）成分としては、特に限定されず公知のものを用いることができる。具体的には、例えば、１−ヒドロキシ−シクロヘキシル−フェニルケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−シクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、４−メチルベンゾフェノン等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。なお、（Ｂ）成分は、紫外線硬化を行なう場合に使用するが、電子線硬化をする場合には、必ずしも必要ではない。（Ｂ）成分を使用する場合の使用量の例としてはが、通常、（Ａ）成分の合計量１００重量部に対し、１〜１０重量部程度等が挙げられるが、この値に限定されるものではない。 The component (B) is not particularly limited, and a known component can be used. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphos Examples include fin oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and 4-methylbenzophenone. That. These may be used alone or in combination of two or more. In addition, although (B) component is used when performing ultraviolet curing, it is not necessarily required when performing electron beam curing. (B) As an example of the usage-amount in the case of using a component, although normally about 1-10 weight part etc. are mentioned with respect to 100 weight part of total amounts of (A) component, It is limited to this value. It is not a thing.
本発明の活性エネルギー線硬化型組成物を用いた硬化被膜の形成方法は、通常、基材として用いるプラスチックフィルムやプラスチックシート等に塗工し乾燥し、活性エネルギー線を照射することにより、フィルム表面上で硬化反応を生じさせれば硬化被膜を形成させればよい。 The method for forming a cured film using the active energy ray-curable composition of the present invention is generally applied to a plastic film or plastic sheet used as a substrate, dried, and irradiated with active energy rays to obtain a film surface. If a curing reaction is caused above, a cured film may be formed.
上記塗工方法としては、例えばバーコーター塗工、ワイヤーバー塗工、メイヤーバー塗工、エアナイフ塗工、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、スクリーン印刷法等が挙げられる。 Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
上記塗工量は、特に限定されないが、通常、乾燥後の重量が０．１〜３０ｇ／ｍ２程度が好ましく、１〜２０ｇ／ｍ２がより好ましい。 The coating amount is not particularly limited, usually, the weight after drying preferably from about 0.1 to 30 g / m 2, more preferably from 1 to 20 g / m 2.
硬化反応に用いる活性エネルギー線としては、例えば紫外線や電子線が挙げられる。紫外線の光源としては、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を使用できる。なお、光量や光源配置、搬送速度等は必要に応じて調整でき、例えば高圧水銀灯を使用する場合には、通常８０〜１６０Ｗ／ｃｍ程度の光量を有するランプ１灯に対して搬送速度５〜５０ｍ／分程度で硬化させるのが好ましい。一方、電子線の場合には、通常１０〜３００ｋＶ程度の加速電圧を有する電子線加速装置にて、搬送速度５〜５０ｍ／分程度で硬化させるのが好ましい。 Examples of active energy rays used for the curing reaction include ultraviolet rays and electron beams. As an ultraviolet light source, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used. The light amount, light source arrangement, transport speed, etc. can be adjusted as necessary. For example, when a high-pressure mercury lamp is used, the transport speed is 5 to 50 m for one lamp having a light amount of about 80 to 160 W / cm. It is preferable to cure at about / min. On the other hand, in the case of an electron beam, it is preferable to cure at an conveyance speed of about 5 to 50 m / min with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV.
以下、実施例及び比較例をあげて本発明を更に詳しく説明するが、本発明がこれらに限定されないことはもとよりである。なお、実施例中、特に説明がない限り、部又は％は重量基準である。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, it cannot be overemphasized that this invention is not limited to these. In the examples, unless otherwise specified, parts or% is based on weight.
なお、本実施例において、重量平均分子量は、ゲルパーメーションクロマトグラフィー（東ソー（株）製、商品名「ＨＬＣ−８２２０」、カラム：東ソー（株）製、商品名「ＴＳＫｇｅｌ ｓｕｐｅｒＨＺ２０００」、「ＴＳＫｇｅｌ ｓｕｐｅｒＨＺＭ−Ｍ」により測定した値を示す。 In this example, the weight average molecular weight is determined by gel permeation chromatography (trade name “HLC-8220” manufactured by Tosoh Corporation, column: manufactured by Tosoh Corporation, trade names “TSKgel superHZ2000”, “TSKgel superHZM”. -M "indicates the value measured.
（活性エネルギー線硬化型樹脂の製造）
実施例１
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ヘキサメチレンジイソシアネートのイソシアヌレート変性体（コロネートＨＸＲ 東ソー社製）（以下、ＨＤＩイソシアヌレートという）２１０部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）を１５００部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ−１）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ−１）成分の（メタ）アクリロイル基当量は１４７ｇ／ｅｑ、ウレタン結合当量７３５ｇ／ｅｑ、重量平均分子量は１５６００であり、固形分１００重量％中のオリゴマー成分の含有率は４３重量％（計算値）であった。この混合物１００部に対し１−ヒドロキシ−シクロヘキシル−フェニルケトン（ＢＡＳＦジャパン（株）製、商品名「イルガキュアー１８４」、以下ＨＣＰＫという）を５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が４１％の活性エネルギー線硬化型組成物を調製した。
(Manufacture of active energy ray-curable resin)
Example 1
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, 210 parts of isocyanurate modified form of hexamethylene diisocyanate (Coronate HXR, manufactured by Tosoh Corporation) (hereinafter referred to as HDI isocyanurate), tin octylate 0. After charging 1500 parts of a mixture of 6 parts dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio 35:65), the temperature in the system was raised to about 80 ° C. over about 1 hour. . Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A-1) and residual monomer (solid content: 100% by weight). The component (A-1) has a (meth) acryloyl group equivalent of 147 g / eq, a urethane bond equivalent of 735 g / eq, a weight average molecular weight of 15600, and the content of the oligomer component in a solid content of 100% by weight is 43% by weight ( Calculated value). 1 part of this mixture is mixed with 5 parts of 1-hydroxy-cyclohexyl-phenylketone (BASF Japan Ltd., trade name “Irgacure 184”, hereinafter referred to as HCPK) at a solid content ratio and diluted with toluene. An active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) with respect to the total organic solid content of 41% was prepared.
実施例２〜６
表１に記載のように、（Ａ−１）〜（Ａ−３）を配合した以外は、実施例１と同様に固形分４０重量％の活性エネルギー線硬化型組成物を調製した。詳細を以下に説明する。
Examples 2-6
As shown in Table 1, an active energy ray-curable composition having a solid content of 40% by weight was prepared in the same manner as in Example 1 except that (A-1) to (A-3) were blended. Details will be described below.
実施例２
上記（Ａ−１）成分９０部に対し、ジペンタエリスリトールヘキサアクリレートを１０部、ＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が３７％の活性エネルギー線硬化型組成物を調製した。
Example 2
To 90 parts of the component (A-1), 10 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK are blended at a solid content ratio, diluted with toluene, solid content of 40% by weight, based on the total organic solid content. An active energy ray-curable composition having a content of component (A) of 37% was prepared.
実施例３
上記（Ａ−１）成分９０部に対し、ペンタエリスリトールテトラアクリレートを１０部、ＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が３７％の活性エネルギー線硬化型組成物を調製した。
Example 3
To 90 parts of the component (A-1), 10 parts of pentaerythritol tetraacrylate and 5 parts of HCPK are blended in a solid content ratio, diluted with toluene, and 40% by weight of solid content (based on the total organic solid content). An active energy ray-curable composition having a content of component A) of 37% was prepared.
実施例４
上記（Ａ−１）成分８０部に対し、ジペンタエリスリトールヘキサアクリレートを２０部、ＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が３３％の活性エネルギー線硬化型組成物を調製した。
Example 4
To 80 parts of the component (A-1), 20 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK are blended at a solid content ratio, diluted with toluene, solid content of 40% by weight, based on the total organic solid content. (A) The active energy ray hardening-type composition whose content rate of a component is 33% was prepared.
実施例５
上記撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ヘキサメチレンジイソシアネートのビウレット変性体（デスモジュールＮ３２００Ａ 住友バイエルウレタン社製）（以下、ＨＤＩビウレットという）２００部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）を１５００部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ−２）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ−２）成分の（メタ）アクリロイル基当量は１４５ｇ／ｅｑ、ウレタン結合当量７２５ｇ／ｅｑ、重量平均分子量は１１０００であり、固形分１００重量％中のオリゴマー成分の含有率は４３重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が４１％の活性エネルギー線硬化型組成物を調製した。
Example 5
In a reaction vessel equipped with the agitator, cooling tube, dropping funnel and nitrogen introduction tube, 200 parts of bimuret modified hexamethylene diisocyanate (Desmodur N3200A manufactured by Sumitomo Bayer Urethane Co., Ltd.) (hereinafter referred to as HDI biuret), tin octylate 0.6 parts of 1500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio 35:65) was added, and the temperature in the system was raised to about 80 ° C. over about 1 hour. Warm up. Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A-2) and residual monomer (solid content: 100% by weight). The component (A-2) has a (meth) acryloyl group equivalent of 145 g / eq, a urethane bond equivalent of 725 g / eq, a weight average molecular weight of 11,000, and the content of the oligomer component in a solid content of 100% by weight is 43% by weight. there were. 100 parts by weight of this mixture is blended with 5 parts of HCPK at a solid content ratio, diluted with toluene, and 40% by weight of solid content and 41% content of component (A) based on the total organic solid content is active energy ray curing. A mold composition was prepared.
実施例６
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、イソホロンジイソシアネートのイソシアヌレート変性体（ＶＥＳＴＡＮＡＴ Ｔ１８９０／１００ エボニック社製）（以下、ＩＰＤＩイソシアヌレートという）６７０部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）を４５００部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ−３）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ−３）成分の（メタ）アクリロイル基当量は１５０ｇ／ｅｑ、ウレタン結合当量７４８ｇ／ｅｑ、重量平均分子量は８５００であり、固形分１００重量％中のオリゴマー成分の含有率は４３重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が４１％の活性エネルギー線硬化型組成物を調製した。
Example 6
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 670 parts of an isocyanurate modified form of isophorone diisocyanate (VESTANAT T1890 / 100 manufactured by Evonik) (hereinafter referred to as IPDI isocyanurate), tin octylate 0 .6 parts, 4500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio 35:65) was charged, and the temperature in the system was raised to about 80 ° C. over about 1 hour. did. Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A-3) and residual monomer (solid content: 100% by weight). The component (A-3) has a (meth) acryloyl group equivalent of 150 g / eq, a urethane bond equivalent of 748 g / eq, a weight average molecular weight of 8500, and a content of the oligomer component in a solid content of 100% by weight is 43% by weight. there were. 100 parts by weight of this mixture is blended with 5 parts of HCPK at a solid content ratio, diluted with toluene, and 40% by weight of solid content and 41% content of component (A) based on the total organic solid content is active energy ray curing. A mold composition was prepared.
実施例７
（Ａ−１）成分４０部に対し、その他の成分としてジペンタエリスリトールヘキサアクリレートを６０部、ＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が１６％の活性エネルギー線硬化型組成物を調製した。
Example 7
(A-1) For 40 parts of component, 60 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK as other components are blended at a solid content ratio, diluted with toluene, solid content of 40% by weight, total organic matter An active energy ray-curable composition having a content of the component (A) with respect to the solid content of 16% was prepared.
実施例８
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ＨＤＩビウレット２００部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）７５０部、ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物（混合比率は、６２：３８）を２４０部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ−４）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ−４）成分の（メタ）アクリロイル基当量は１５６ｇ／ｅｑ、ウレタン結合当量６１２ｇ／ｅｑ、重量平均分子量は１０５００であり、固形分１００重量％中のオリゴマー成分の含有率は５８重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が５５％の活性エネルギー線硬化型組成物を調製した。
Example 8
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 200 parts of HDI biuret, 0.6 parts of tin octylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65) After adding 750 parts, 240 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing ratio 62:38), the temperature in the system was raised to about 80 ° C. over about 1 hour. Warm up. Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A-4) and residual monomer (solid content: 100% by weight). The component (A-4) has a (meth) acryloyl group equivalent of 156 g / eq, a urethane bond equivalent of 612 g / eq, a weight average molecular weight of 10,500, and the content of the oligomer component in a solid content of 100% by weight is 58% by weight. there were. 100 parts by weight of this mixture is blended with 5 parts of HCPK at a solid content ratio, diluted with toluene, and 40% by weight of solid content and active energy ray curing with a content of component (A) of 55% of the total organic solid content. A mold composition was prepared.
実施例９
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ＨＤＩイソシアヌレート変性体の多量体（コロネートＨＫ 東ソー社製）２０５部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）を１５００部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ−５）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ−５）成分の（メタ）アクリロイル基当量は１５０ｇ／ｅｑ、ウレタン結合当量７５０ｇ／ｅｑ、重量平均分子量は４６０００であり、固形分１００重量％中のオリゴマー成分の含有率は４３重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が４１％の活性エネルギー線硬化型組成物を調製した。
Example 9
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 205 parts of an HDI isocyanurate modified product (Coronate HK manufactured by Tosoh Corporation), 0.6 parts of tin octylate, dipentaerythritol pentaacrylate And a mixture of dipentaerythritol hexaacrylate (mixing ratio: 35:65) was charged in 1500 parts, and the system temperature was raised to about 80 ° C. over about 1 hour. Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A-5) and residual monomer (solid content: 100% by weight). The (meth) acryloyl group equivalent of the component (A-5) is 150 g / eq, the urethane bond equivalent is 750 g / eq, the weight average molecular weight is 46000, and the content of the oligomer component in the solid content of 100% by weight is 43% by weight. there were. 100 parts by weight of this mixture is blended with 5 parts of HCPK at a solid content ratio, diluted with toluene, and 40% by weight of solid content and 41% content of component (A) based on the total organic solid content is active energy ray curing. A mold composition was prepared.
実施例１０
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ＨＤＩビウレット６７０部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）のジペンタエリスリトールペンタアクリレートにカプロラクトン２ｍｏｌを付加させた成分を１７２８部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ−６）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ−６）成分の（メタ）アクリロイル基当量は１９６ｇ／ｅｑ、ウレタン結合当量９７６ｇ／ｅｑ、重量平均分子量は１３５００であり、固形分１００重量％中のオリゴマー成分の含有率は４９重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が４７％の活性エネルギー線硬化型組成物を調製した。
Example 10
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 670 parts of HDI biuret, 0.6 part of tin octylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65) After adding 1728 parts of a component obtained by adding 2 mol of caprolactone to dipentaerythritol pentaacrylate, the temperature in the system was raised to about 80 ° C. over about 1 hour. Next, the reaction system was kept at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A-6) and residual monomer (solid content: 100% by weight). The component (A-6) has a (meth) acryloyl group equivalent of 196 g / eq, a urethane bond equivalent of 976 g / eq, a weight average molecular weight of 13500, and the content of the oligomer component in a solid content of 100% by weight is 49% by weight. there were. 100 parts by weight of this mixture is blended with 5 parts of HCPK in a solid content ratio, diluted with toluene, and 40% by weight of solid content, and the content of component (A) based on the total organic solid content is 47%. A mold composition was prepared.
比較例１
上記（Ａ−１）成分２０部に対し、その他の成分としてジペンタエリスリトールヘキサアクリレートを８０部、ＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が８％の活性エネルギー線硬化型組成物を調製した。
Comparative Example 1
With respect to 20 parts of the component (A-1), 80 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK as other ingredients are blended at a solid content ratio, diluted with toluene, and 40% by weight of solid content, An active energy ray-curable composition in which the content of the component (A) relative to the organic solid content was 8% was prepared.
比較例２〜７
表１に記載のように、（Ａ−２）及び（Ａ’−７）〜（Ａ’−１１）を配合した以外は、比較例１と同様に固形分４０重量％の活性エネルギー線硬化型組成物を調製した。詳細を以下に説明する。
Comparative Examples 2-7
As shown in Table 1, the active energy ray-curable type having a solid content of 40% by weight is the same as Comparative Example 1 except that (A-2) and (A′-7) to (A′-11) are blended. A composition was prepared. Details will be described below.
比較例２
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ＨＤＩビウレット２００部、オクチル酸スズ０．６部、ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物（混合比率は、６２：３８）を４８０部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ’−７）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ’−７）成分の（メタ）アクリロイル基当量は１６６ｇ／ｅｑ、ウレタン結合当量４９８ｇ／ｅｑ、重量平均分子量は８０００であり、固形分１００重量％中のオリゴマー成分の含有率は７３重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が０％の活性エネルギー線硬化型組成物を調製した。
Comparative Example 2
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 200 parts of HDI biuret, 0.6 part of tin octylate, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing ratio is 62: After charging 480 parts of 38), the temperature in the system was raised to about 80 ° C. over about 1 hour. Next, the reaction system was maintained at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A′-7) and residual monomer (solid content: 100% by weight). The component (A'-7) has a (meth) acryloyl group equivalent of 166 g / eq, a urethane bond equivalent of 498 g / eq, a weight average molecular weight of 8,000, and a content of the oligomer component in a solid content of 100% by weight is 73% by weight. Met. 100 parts by weight of this mixture is blended with 5 parts of HCPK in a solid content ratio, diluted with toluene, and 40% by weight of solid content and 0% active energy ray curing with respect to the total organic solid content. A mold composition was prepared.
比較例３
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ＨＤＩイソシアヌレート２００部、オクチル酸スズ０．６部、２−ヒドロキシエチルアクリレートを１５０部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ’−８）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ’−８）成分の（メタ）アクリロイル基当量は３４４ｇ／ｅｑ、ウレタン結合当量３４４ｇ／ｅｑ、重量平均分子量は２３００であり、固形分１００重量％中のオリゴマー成分の含有率は９８重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が０％の活性エネルギー線硬化型組成物を調製した。
Comparative Example 3
After charging 200 parts of HDI isocyanurate, 0.6 parts of tin octylate and 150 parts of 2-hydroxyethyl acrylate in a reaction vessel equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introducing pipe, it took about 1 hour. The temperature in the system was raised to about 80 ° C. Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A′-8) and residual monomer (solid content: 100% by weight). The component (A′-8) has a (meth) acryloyl group equivalent of 344 g / eq, a urethane bond equivalent of 344 g / eq, a weight average molecular weight of 2300, and the content of the oligomer component in a solid content of 100% by weight is 98% by weight. Met. 100 parts by weight of this mixture is blended with 5 parts of HCPK in a solid content ratio, diluted with toluene, and 40% by weight of solid content and 0% active energy ray curing with respect to the total organic solid content. A mold composition was prepared.
比較例４
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ＨＤＩイソシアヌレート２１０部、オクチル酸スズ０．６部、２−ヒドロキシエチルアクリレートを１１０部と２−ヒドロキシエチルアクリレートのカプロラクトン５ｍｏｌ付加物を１８０部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ’−９）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ’−９）成分の（メタ）アクリロイル基当量は４９０ｇ／ｅｑ、ウレタン結合当量４９０ｇ／ｅｑ、重量平均分子量は４３００であり、固形分１００重量％中のオリゴマー成分の含有率は９８重量％であった。この混合物１００部に対し１−ヒドロキシ−シクロヘキシル−フェニルケトン（ＢＡＳＦジャパン（株）製、商品名「イルガキュアー１８４」、以下ＨＣＰＫという）を５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が０％の活性エネルギー線硬化型組成物を調製した。
Comparative Example 4
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 210 parts of HDI isocyanurate, 0.6 part of tin octylate, 110 parts of 2-hydroxyethyl acrylate and 5 mol of caprolactone of 2-hydroxyethyl acrylate After adding 180 parts of the adduct, the temperature in the system was raised to about 80 ° C. over about 1 hour. Next, the reaction system was maintained at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A′-9) and residual monomer (solid content: 100% by weight). The component (A′-9) has a (meth) acryloyl group equivalent of 490 g / eq, a urethane bond equivalent of 490 g / eq, a weight average molecular weight of 4300, and the content of the oligomer component in a solid content of 100% by weight is 98% by weight. Met. 1 part of this mixture is mixed with 5 parts of 1-hydroxy-cyclohexyl-phenylketone (BASF Japan Ltd., trade name “Irgacure 184”, hereinafter referred to as HCPK) at a solid content ratio and diluted with toluene. An active energy ray-curable composition having a solid content of 40% by weight and a content of the component (A) based on the total organic solid content of 0% was prepared.
比較例５
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ヘキサメチレンジイソシアネートのアロファネート体（タケネート Ｄ−１７８ＮＬ 三井化学社製）（以下、ＨＤＩアロファネートという）２６０部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）を１５００部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ’−１０）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ’−１０）成分の（メタ）アクリロイル基当量は１５７ｇ／ｅｑ、ウレタン結合当量７８５ｇ／ｅｑ、重量平均分子量は４０００であり、固形分１００重量％中のオリゴマー成分の含有率は４５重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が０％の活性エネルギー線硬化型組成物を調製した。
Comparative Example 5
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 260 parts of hexamethylene diisocyanate allophanate (Takenate D-178NL, manufactured by Mitsui Chemicals, Inc.) (hereinafter referred to as HDI allophanate), 0. After charging 1500 parts of a mixture of 6 parts dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio 35:65), the temperature in the system was raised to about 80 ° C. over about 1 hour. . Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A′-10) and residual monomer (solid content: 100% by weight). The component (A′-10) has a (meth) acryloyl group equivalent of 157 g / eq, a urethane bond equivalent of 785 g / eq, a weight average molecular weight of 4000, and a content of the oligomer component in a solid content of 100% by weight is 45% by weight. Met. 100 parts by weight of this mixture is blended with 5 parts of HCPK in a solid content ratio, diluted with toluene, and 40% by weight of solid content and 0% active energy ray curing with respect to the total organic solid content. A mold composition was prepared.
比較例６
撹拌装置、冷却管、滴下ロート及び窒素導入管を備えた反応容器に、ヘキサメチレンジイソシアネート１７０部、オクチル酸スズ０．６部、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（混合比率は、３５：６５）を１５００部仕込んだ後、約１時間かけて、系内の温度を約８０℃に昇温した。次いで、同温度において、反応系を２時間保持した後、冷却して、活性エネルギー線硬化型オリゴマー（Ａ’−１１）と残存モノマーの混合物（固形分１００重量％）を得た。（Ａ’−１１）成分の（メタ）アクリロイル基当量は１２２ｇ／ｅｑ、ウレタン結合当量６１０ｇ／ｅｑ、重量平均分子量は３２００であり、固形分１００重量％中のオリゴマー成分の含有率は４２重量％であった。この混合物１００部に対しＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が０％の活性エネルギー線硬化型組成物を調製した。
Comparative Example 6
In a reaction vessel equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 170 parts of hexamethylene diisocyanate, 0.6 parts of tin octylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio is 35:65), and the temperature inside the system was raised to about 80 ° C. over about 1 hour. Next, the reaction system was held at the same temperature for 2 hours and then cooled to obtain a mixture of active energy ray-curable oligomer (A′-11) and residual monomer (solid content: 100% by weight). The (A′-11) component has a (meth) acryloyl group equivalent of 122 g / eq, a urethane bond equivalent of 610 g / eq, a weight average molecular weight of 3200, and a content of the oligomer component in a solid content of 100% by weight is 42% by weight. Met. 100 parts by weight of this mixture is blended with 5 parts of HCPK in a solid content ratio, diluted with toluene, and 40% by weight of solid content and 0% active energy ray curing with respect to the total organic solid content. A mold composition was prepared.
比較例７
（Ａ−２）成分２５部に対し、（Ａ’−１０）成分を７５部、ＨＣＰＫを５部、固形分割合で配合し、トルエンで希釈して、固形分４０重量％、全有機物固形分に対する（Ａ）成分の含有率が１０％の活性エネルギー線硬化型組成物を調製した。
Comparative Example 7
(A-2) 75 parts of component (A′-10) and 5 parts of HCPK are mixed at a solid content ratio with 25 parts of component, diluted with toluene, solid content of 40% by weight, total organic solid content The active energy ray hardening-type composition whose content rate of (A) component with respect to 10% was prepared.
＜組成物のトルエン希釈Ｅ型粘度＞
各実施例・比較例における固形分のみを配合した混合物（即ち、（１）各実施例・比較例で製造された活性エネルギー線硬化型組成物及び残存モノマーの混合物と、（２）ＨＣＰＫなどの活性エネルギー線硬化型組成物に含有可能なほかの固形分とを含有してなる混合物）に対してトルエンにて重量％で固形分８０％へ希釈した溶液の粘度を２５℃でＥ型粘度計（東機産業社製 ＴＶ−２２ ３°コーン）にて測定した。測定方法は、約０．４ｍＬを測定用試料とし、回転速度０．５〜１００ｒｐｍ、５分間回転の条件で組成物のトルエン希釈Ｅ型粘度（ｍＰａ・ｓ）とした。
<Toluene diluted E-type viscosity of composition>
Mixtures containing only solids in each Example / Comparative Example (that is, (1) a mixture of active energy ray-curable composition and residual monomer produced in each Example / Comparative Example, and (2) HCPK, etc. E-type viscometer at 25 ° C. with a viscosity of a solution diluted with toluene to 80% solids by weight with respect to a mixture containing other solids that can be contained in the active energy ray-curable composition) (Toki Sangyo TV-22 3 ° cone). About 0.4 mL of the measurement method was used as a measurement sample, and the toluene-diluted E-type viscosity (mPa · s) of the composition was measured under a rotation speed of 0.5 to 100 rpm for 5 minutes.
＜硬化被膜の作成＞
１００μｍ膜厚の環状オレフィン樹脂系フィルム上に、各活性エネルギー線硬化型組成物を、硬化後の被膜の膜厚が５μｍとなるように＃１０バーコーターにて塗布し、７０℃で１分乾燥させてフィルムを作製した。次いで、得られたフィルムを紫外線硬化装置（製品名：ＵＢＴ−０８０−７Ａ／ＢＭ、（株）マルチプライ製、高圧水銀灯６００ｍＪ／ｃｍ２））を使用し、硬化被膜を供えたプラスチックフィルムを得た。実施例２〜１０、及び比較例１〜７に係る樹脂組成物についても同様にフィルム作成し、以下のように硬化被膜を評価した。結果を表１及び表２に示す。
<Creation of cured film>
Each active energy ray-curable composition was applied on a 100 μm-thick cyclic olefin resin film with a # 10 bar coater so that the film thickness after curing was 5 μm, and dried at 70 ° C. for 1 minute. To produce a film. Next, the obtained film was used with an ultraviolet curing device (product name: UBT-080-7A / BM, manufactured by Multiply, high pressure mercury lamp 600 mJ / cm 2 ) to obtain a plastic film provided with a cured film. It was. Films were similarly prepared for the resin compositions according to Examples 2 to 10 and Comparative Examples 1 to 7, and cured films were evaluated as follows. The results are shown in Tables 1 and 2.
＜硬化被膜の評価＞
（１）塗工性
上記で得られた評価用フィルムを目視で観察し、液ハジキ発生の有無を確認した。
○：ハジキなし
△：一部に液ハジキが見られる
×：全面にハジキが見られる
<Evaluation of cured film>
(1) Coating property The film for evaluation obtained above was visually observed to confirm the presence or absence of liquid repellency.
○: No repelling △: Some liquid repelling is seen ×: Repelling is seen on the entire surface
（２）密着性
上記で得られた評価用フィルムに対し、ＪＩＳ Ｋ５６００−５−４に準じ、１００マス碁盤目剥離試験により、硬化被膜の密着性を評価した。
結果の表示は（剥離試験で残ったマス目の数／１００）
(2) Adhesiveness The adhesiveness of the cured film was evaluated by a 100 square cross peel test on the evaluation film obtained above in accordance with JIS K5600-5-4.
The result is displayed (number of cells remaining in peel test / 100)
（３）耐擦傷性
上記で得られた評価用フィルムに対し、スチールウール（＃００００、１０ｍｍ×１０ｍｍ）を底に貼り付けた３００ｇの重りで１０往復擦り、塗工外観を以下の基準で目視評価した。
○：傷なし
○−：５本以下の傷が発生
△：６本以上２０本以下の傷が発生
×：多数の傷が発生
(3) Scratch resistance The evaluation film obtained above was rubbed 10 reciprocally with a 300 g weight with steel wool (# 0000, 10 mm × 10 mm) attached to the bottom, and the coating appearance was visually observed according to the following criteria. evaluated.
○: No scratch ○-: 5 or less scratches occurred Δ: 6 to 20 scratches occurred ×: Many scratches occurred
表１及び表２中、組成数値は重量部数を表す。
ＨＤＩイソシアヌレート：ヘキサメチレンジイソシアネートのイソシアヌレート変性体
ＨＤＩビウレット：ヘキサメチレンジイソシアネートのビウレット変性体
ＨＤＩアロファネート：ヘキサメチレンジイソシアネートのアロファネート変性体
ＩＰＤＩイソシアヌレート：イソホロンジイソシアネートのイソシアヌレート変性体
In Tables 1 and 2, compositional values represent parts by weight.
HDI isocyanurate: isocyanurate modified of hexamethylene diisocyanate HDI biuret: biuret modified of hexamethylene diisocyanate HDI allophanate: allophanate modified of hexamethylene diisocyanate IPDI isocyanurate: isocyanurate modified of isophorone diisocyanate
Claims (6)
全有機物固形分に対して活性エネルギー線硬化型オリゴマー（Ａ）を１５〜８０重量％含有し、
該（Ａ）成分は、（１）（メタ）アクリロイル基、（２）ポリペンタエリスリトール骨格並びに（３）イソシアヌレート基及び／又はビウレット基を有し、重量平均分子量（Ｍｗ）が３０００〜１０００００、ウレタン結合当量が３５０〜２０００ｇ／ｅｑ、（メタ）アクリロイル当量が１２０〜２５０ｇ／ｅｑである、活性エネルギー線硬化型組成物。 The E-type viscosity at 25 ° C. when the total solid content is diluted with toluene to 80% solid content by weight is 300 to 10,000 mPa · s,
Containing 15 to 80% by weight of active energy ray-curable oligomer (A) based on the total organic solid content,
The component (A) has (1) (meth) acryloyl group, (2) polypentaerythritol skeleton, and (3) isocyanurate group and / or biuret group, and has a weight average molecular weight (Mw) of 3000 to 100,000. An active energy ray-curable composition having a urethane bond equivalent of 350 to 2000 g / eq and a (meth) acryloyl equivalent of 120 to 250 g / eq.
The coating film of Claim 4 or 5 in which the said base material has not performed the easily bonding process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016066838 | 2016-03-29 | ||
| JP2016066838 | 2016-03-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017179368A true JP2017179368A (en) | 2017-10-05 |
| JP6504528B2 JP6504528B2 (en) | 2019-04-24 |
Family
ID=60003763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017062960A Active JP6504528B2 (en) | 2016-03-29 | 2017-03-28 | Active energy ray curable composition and coating film |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6504528B2 (en) |
| KR (1) | KR102285267B1 (en) |
| CN (1) | CN107365554B (en) |
| TW (1) | TWI715751B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190111809A (en) | 2018-03-23 | 2019-10-02 | 아라까와 가가꾸 고교 가부시끼가이샤 | Active energy ray curable resin composition for hard coat, cured film, laminate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019013082A1 (en) * | 2017-07-13 | 2019-01-17 | リンテック株式会社 | Hardcoat agent and layered film |
| CN112004850B (en) * | 2018-04-27 | 2024-01-19 | 三菱化学株式会社 | Curable composition, cured product, and laminate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002285083A (en) * | 2001-03-28 | 2002-10-03 | Mitsubishi Chemicals Corp | Active energy ray-curable anchor coating composition and coating film forming method |
| JP2008248069A (en) * | 2007-03-30 | 2008-10-16 | Sanyo Chem Ind Ltd | Active energy ray-curable resin composition for hard-coating use |
| WO2010146801A1 (en) * | 2009-06-17 | 2010-12-23 | 日本化薬株式会社 | Urethane (meth)acrylate compound and resin composition containing same |
| JP2011157497A (en) * | 2010-02-02 | 2011-08-18 | Daicel-Cytec Co Ltd | Active energy ray-curable composition |
| WO2014061539A1 (en) * | 2012-10-17 | 2014-04-24 | 第一工業製薬株式会社 | Urethane acrylate, and reactive composition containing same |
| JP2016204585A (en) * | 2015-04-28 | 2016-12-08 | 富士フイルム株式会社 | Curable composition, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030077394A1 (en) * | 2001-08-28 | 2003-04-24 | Bradford Christophen J. | Dual cure coating composition and process for using the same |
| KR100724797B1 (en) * | 2005-10-10 | 2007-06-04 | 에스에스씨피 주식회사 | High solid UV curable coating composition comprising a low viscosity polyfunctional urethane acrylate oligomer |
| JP2009286924A (en) | 2008-05-30 | 2009-12-10 | Jsr Corp | Curable composition |
| JP2010235809A (en) * | 2009-03-31 | 2010-10-21 | Sumitomo Chemical Co Ltd | Curable paint, scratch-resistant resin plate, and display window protection plate for portable information terminal |
| JP2014189566A (en) | 2013-03-26 | 2014-10-06 | Dic Corp | Active energy ray-curable composition for cyclic olefin resin and cyclic olefin resin film using the composition |
-
2017
- 2017-03-28 KR KR1020170039019A patent/KR102285267B1/en active Active
- 2017-03-28 JP JP2017062960A patent/JP6504528B2/en active Active
- 2017-03-29 TW TW106110449A patent/TWI715751B/en not_active IP Right Cessation
- 2017-03-29 CN CN201710196549.6A patent/CN107365554B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002285083A (en) * | 2001-03-28 | 2002-10-03 | Mitsubishi Chemicals Corp | Active energy ray-curable anchor coating composition and coating film forming method |
| JP2008248069A (en) * | 2007-03-30 | 2008-10-16 | Sanyo Chem Ind Ltd | Active energy ray-curable resin composition for hard-coating use |
| WO2010146801A1 (en) * | 2009-06-17 | 2010-12-23 | 日本化薬株式会社 | Urethane (meth)acrylate compound and resin composition containing same |
| JP2011157497A (en) * | 2010-02-02 | 2011-08-18 | Daicel-Cytec Co Ltd | Active energy ray-curable composition |
| WO2014061539A1 (en) * | 2012-10-17 | 2014-04-24 | 第一工業製薬株式会社 | Urethane acrylate, and reactive composition containing same |
| JP2016204585A (en) * | 2015-04-28 | 2016-12-08 | 富士フイルム株式会社 | Curable composition, cured film, organic EL display device, liquid crystal display device, touch panel and touch panel display device |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190111809A (en) | 2018-03-23 | 2019-10-02 | 아라까와 가가꾸 고교 가부시끼가이샤 | Active energy ray curable resin composition for hard coat, cured film, laminate |
| JP2019167524A (en) * | 2018-03-23 | 2019-10-03 | 荒川化学工業株式会社 | Resin composition for active energy ray-curable hard coat, cured film, and laminate |
| JP7044087B2 (en) | 2018-03-23 | 2022-03-30 | 荒川化学工業株式会社 | Resin composition for active energy ray-curable hard coat, cured film, laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102285267B1 (en) | 2021-08-02 |
| KR20170113306A (en) | 2017-10-12 |
| CN107365554B (en) | 2021-01-08 |
| JP6504528B2 (en) | 2019-04-24 |
| CN107365554A (en) | 2017-11-21 |
| TW201807113A (en) | 2018-03-01 |
| TWI715751B (en) | 2021-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101854524B1 (en) | Hard Coating Film and Flexible Display Having the Same | |
| CN102803332B (en) | Urethane (meth) acrylate compound and resin composition containing same | |
| KR100998116B1 (en) | Active energy ray-curable resin composition, preparation method thereof and coating composition using same | |
| JP2023167591A (en) | Resin composition for hue adjustment and optical laminate including the same | |
| CN108137761A (en) | Active energy ray-curable resin composition, active energy ray curable emulsion compositions and coating agent composition | |
| US20180002463A1 (en) | Coating composition and coating film preparaed therefrom | |
| JP6845586B2 (en) | Active energy ray-curable coating agent | |
| CN104039850B (en) | Active energy ray-curable resin composition | |
| JP7024729B2 (en) | Active energy ray-curable resin composition and laminated film | |
| JP6504528B2 (en) | Active energy ray curable composition and coating film | |
| KR20130074830A (en) | Anti-blocking hardcoating composition and hard coating layer for anti-blocking | |
| JP5839250B1 (en) | Curable composition, cured product thereof, molded article and display member | |
| KR20100110724A (en) | Resin composition | |
| JP7214946B1 (en) | Active energy ray-curable hard coating agents, hard coating layers, laminates, and substrates with inorganic oxide films | |
| JP6565276B2 (en) | Curable composition, cured product and laminate | |
| TWI510531B (en) | Plastic film | |
| KR20200140295A (en) | Curable resin composition | |
| TW201446844A (en) | Resin film and method for producing same | |
| CN108727556B (en) | Urethane (meth) acrylate, active energy ray-curable resin composition, cured product, and film | |
| TWI736777B (en) | Urethane (meth)acrylate, active energy ray curable resin composition, cured product and film | |
| WO2022014558A1 (en) | Urethane (meth)acrylate composition, active energy ray-curable composition, and cured product thereof | |
| KR20140083267A (en) | Coating composition for anti-glare, anti-glare film using the same | |
| KR20160116923A (en) | Anti-Static Hard Coating Composition and Optical Sheet Using the Same | |
| JP2016121206A (en) | Active energy ray-curable resin composition, paint containing the same, coating film thereof, and laminated film having the coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171101 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180912 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181001 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181102 |
|
| 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: 20190304 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6504528 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190317 |
|
| 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 |