CN109134816A - Carbamate (methyl) acrylate, activity energy-line solidifying type resin composition, solidfied material and film - Google Patents
Carbamate (methyl) acrylate, activity energy-line solidifying type resin composition, solidfied material and film Download PDFInfo
- Publication number
- CN109134816A CN109134816A CN201810606583.0A CN201810606583A CN109134816A CN 109134816 A CN109134816 A CN 109134816A CN 201810606583 A CN201810606583 A CN 201810606583A CN 109134816 A CN109134816 A CN 109134816A
- Authority
- CN
- China
- Prior art keywords
- methyl
- acrylate
- carbamate
- type resin
- film
- 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
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- GNBCKKSGQPLTRW-UHFFFAOYSA-N C(C=C)(=O)OC.C(N)(O)=O Chemical compound C(C=C)(=O)OC.C(N)(O)=O GNBCKKSGQPLTRW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000000694 effects Effects 0.000 title claims abstract description 40
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 21
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 89
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 64
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 34
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical group 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000008096 xylene Substances 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- -1 Isocyanuric acid ester Chemical class 0.000 claims description 50
- 239000002216 antistatic agent Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 239000010408 film Substances 0.000 description 53
- 239000000047 product Substances 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 210000002469 basement membrane Anatomy 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 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 6
- GISWNRNUVGGVOS-UHFFFAOYSA-N 3,4-dihydroxybutan-2-yl prop-2-enoate Chemical compound OCC(O)C(C)OC(=O)C=C GISWNRNUVGGVOS-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer 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
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- CTLDMRCJDQGAQJ-UHFFFAOYSA-N (1,1-dimethoxy-2-phenylethyl)benzene Chemical compound C=1C=CC=CC=1C(OC)(OC)CC1=CC=CC=C1 CTLDMRCJDQGAQJ-UHFFFAOYSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- YYJIYUNJTKCRHL-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC(=O)C=C YYJIYUNJTKCRHL-UHFFFAOYSA-N 0.000 description 1
- 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
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- 150000000094 1,4-dioxanes Chemical class 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RLYCQMBTFVUJTR-UHFFFAOYSA-N 2-(hydroxymethylidene)-5-phenoxypentanoic acid Chemical compound OC=C(C(O)=O)CCCOC1=CC=CC=C1 RLYCQMBTFVUJTR-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
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- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- KVLBDHNRYNADNI-UHFFFAOYSA-N 5-hydroxy-6-methoxy-2-methylhex-2-enoic acid Chemical compound COCC(O)CC=C(C)C(O)=O KVLBDHNRYNADNI-UHFFFAOYSA-N 0.000 description 1
- RZLDFOKIYOYQOM-UHFFFAOYSA-N 5-methylhept-5-en-1-ol Chemical group CC=C(C)CCCCO RZLDFOKIYOYQOM-UHFFFAOYSA-N 0.000 description 1
- BAQTZFHVKJOFMI-UHFFFAOYSA-N 5-methylhept-5-en-2-ol Chemical group CC=C(C)CCC(C)O BAQTZFHVKJOFMI-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
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- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- DVQGYGDSAGBRSZ-UHFFFAOYSA-N bis(1-cyclohexylcyclohexa-2,4-dien-1-yl)methanone Chemical compound C1C=CC=CC1(C1CCCCC1)C(=O)C1(C2CCCCC2)CC=CC=C1 DVQGYGDSAGBRSZ-UHFFFAOYSA-N 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- 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
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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polymerisation Methods In General (AREA)
Abstract
[technical problem] the present invention provides carbamate (methyl) acrylate, activity energy-line solidifying type resin composition, solidfied material and films.[technological means] the present invention provides carbamate (methyl) acrylate, carbamate (methyl) acrylate is the reaction product of the compound group containing following (A) and (B): polyisocyanates (A), is the polymer of xylene diisocyanate；And (methyl) acrylate (B) containing hydroxyl.The film of the solidfied material of activity energy-line solidifying type resin composition containing above-mentioned carbamate (methyl) acrylate, has both high refractive index, high rigidity, low crimpiness and high-light-fastness.
Description
Technical field
The present invention relates to carbamate (methyl) acrylate, activity energy-line solidifying type resin composition, solidfied material
And film.
Background technique
A large amount of optical films such as prismatic lens, index matching (IM) film, antireflection film have been used in liquid crystal display.Above-mentioned film
In, from the viewpoint of high brightness, anti-skeleton visibility (bone is shown in preventing property of え), counnter attack photosensitiveness adjustment, it is desirable that for high refraction
Rate resin material.High refractive index resins material is, for example, using (patent documents such as the substances of polymerizable monomer with fluorene skeleton
1)。
Existing technical literature
Patent document
[patent document 1] Japanese Unexamined Patent Publication 2010-007004 bulletin
Summary of the invention
Technical problems to be solved by the inivention
It is different depending on the application, it is desirable that a variety of different physical properties in activity energy-line solidifying type resin composition.This hair
It is bright that the technical problem to be solved is that provide to be formed on the surface of basement membrane to have both high refractive index, high rigidity, low crimpiness and height
The activity energy-line solidifying type resin composition of sunproof solidified material layer.
Solve the technological means of technical problem
Present inventor concentrates on studies to solve aforementioned technical problem, finds by using the reaction with specific structure
Product can solve aforementioned technical problem, so as to complete the present invention.
Following items are provided through the invention.
(project 1)
Carbamate (methyl) acrylate, carbamate (methyl) acrylate be containing following (A) and
(B) reaction product of compound group:
Polyisocyanates (A) is the polymer of xylene diisocyanate；And
(methyl) acrylate (B) containing hydroxyl.
(project 2)
Carbamate (methyl) acrylate as described in above-mentioned project, the polyisocyanates (A) are dimethylbenzene two
Isocyanuric acid ester polymer, biuret polymer or the addition polymer of isocyanates.
(project 3)
Activity energy-line solidifying type resin composition, the activity energy-line solidifying type resin composition contain such as above-mentioned item
Carbamate described in any one of mesh (methyl) acrylate.
(project 4)
Activity energy-line solidifying type resin composition as described in above-mentioned project, the active energy ray-curable resin group
It closes object and contains Photoepolymerizationinitiater initiater.
(project 5)
Activity energy-line solidifying type resin composition as described in any one of above-mentioned project, the active energy line curing
Type resin combination contains polymerizable monomer.
(project 6)
Activity energy-line solidifying type resin composition as described in any one of above-mentioned project, the active energy line curing
Type resin combination contains antistatic agent.
(project 7)
The solidfied material of activity energy-line solidifying type resin composition as described in any one of above-mentioned project.
(project 8)
Film containing the solidfied material as described in above-mentioned project.
In the present invention, it for said one or multiple features, other than the combination expressed, can also provide further
Combination.
Beneficial effect
By using activity energy-line solidifying type resin composition provided by the present invention, can be formed on the surface of basement membrane
Have both the solidified material layer (cured film) of high refractive index, high rigidity, low crimpiness and high-light-fastness.
Specific embodiment
Among full text of the present invention, the range of the numerical value such as value and content of each physical property can suitably set (such as from
It is selected in the value of upper and lower bound documented by following projects).Specifically, for numerical value α, numerical value α the upper limit for example
Be A1, A2, A3 etc., numerical value α lower limit be, for example, B1, B2, B3 etc. in the case where, the range of numerical value α be, for example, A1 or less, A2 with
Under, A3 or less, B1 or more, B2 or more, B3 or more, A1~B1, A1~B2, A1~B3, A2~B1, A2~B2, A2~B3, A3
~B1, A3~B2, A3~B3 etc..
[carbamate (methyl) acrylate]
The present invention provides carbamate (methyl) acrylate, carbamate (methyl) acrylate is to contain
There is the reaction product of the compound group of following (A) and (B):
Polyisocyanates (A) is the polymer of xylene diisocyanate；And
(methyl) acrylate (B) containing hydroxyl.
In the present invention, " (methyl) acrylic acid " refers to " in the group being made of acrylic acid and methacrylic acid
It is at least one ".Similarly, " (methyl) acrylate " refers to " selected from the group being made of acrylate and methacrylate
At least one of ".Furthermore " (methyl) acryloyl group " refers to " selected from the group being made of acryloyl group and methylacryloyl
At least one of ".
< polyisocyanates (A) is the polymer of xylene diisocyanate；Also referred to as polyisocyanates (A), (A) at
Point >
In the present invention, " polyisocyanates " refers to the chemical combination with more than two isocyanate group (- N=C=O)
Object.
Polyisocyanates (A) can be used alone, and two or more merging can also be used.In one embodiment,
Polyisocyanates (A) is isocyanuric acid ester polymer, biuret polymer or the addition polymer of xylene diisocyanate.
Isocyanuric acid ester polymer such as following structural formula (A-1) compound represented of xylene diisocyanate etc..
[changing 1]
(in formula, n1 is 0 or more integer, and n1 is preferably 0~3).
Biuret polymer such as following structural formula (A-2) compound represented of xylene diisocyanate etc..
[changing 2]
(in formula, n2 is 0 or more integer, and n2 is preferably 0~3).
Trimethylolpropane and two shown in the addition polymer such as following structural formula (A-3) of xylene diisocyanate
The addition product of toluene di-isocyanate(TDI),
[changing 3]
(in formula, n3 is 0 or more integer, and n3 is preferably 0~3).
Glycerol and the addition product of xylene diisocyanate etc. shown in following structural formula (A-4).
[changing 4]
(in formula, n4 is 0 or more integer, and n4 is preferably 0~3).
In addition, structure above is only an example, the present invention is not intended to be limited to the change indicated by structure above
Close object.
" polymer of xylene diisocyanate " so-called in the present invention indicates the compound of dimer or more.Dimethylbenzene two
The degree of polymerization upper limit of the polymer of isocyanates is, for example, 12,11,10,9,8,7,6,5,4 etc., lower limit is, for example, 11,10,9,
8,7,6,5,4,3 etc..In one embodiment, the degree of polymerization is preferably 3~12, and further preferably 3~9.In addition, usually may be used
The polymer of purchase is the polymer mixture of different polymers, and the degree of polymerization is average value, i.e., is indicated with average degree of polymerization.It is flat
The right preferred value of homopolymerization is identical as the preferred value of the above-mentioned degree of polymerization.In addition, the degree of polymerization of n aggressiveness is n in the present invention.
The value of the weight average molecular weight (Mw) of polyisocyanates (A) is not particularly limited.Polyisocyanates (A's) divides equally again
The upper limit of son amount (Mw) is, for example, 80000,70000,60000,50000,40000,30000,20000,10000,9000,
8000,7000,6000,5000,4000,3000,2000,1500,1000,600 etc., lower limit is, for example, 70000,60000,
50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、 4000、3000、2000、1500、
1000,600,500 etc..In one embodiment, from the viewpoint of the productivity of carbamate (methyl) acrylate,
The weight average molecular weight (Mw) of polyisocyanates (A) is preferably 500~50000, and further preferably 600~50000.
The value of the number-average molecular weight (Mn) of polyisocyanates (A) is not particularly limited.The equal molecule of number of polyisocyanates (A)
The upper limit of amount (Mn) is, for example, 60000,50000,40000,30000,20000,10000,9000,8000,7000,6000,
5000,4000,3000,2000,1000,600,500,300 etc., lower limit is, for example, 55000,50000,40000,35000,
30000,20000,10000,9000,8000,7000,6000,5000,4000,3000,2000,1000,500 etc..In a reality
It applies in mode, from the viewpoint of the productivity of carbamate (methyl) acrylate, the equal molecule of number of polyisocyanates (A)
Measuring (Mn) is preferably 500~60000, and further preferably 500~40000.
The upper limit of the molecular weight distribution (Mw/Mn) of polyisocyanates (A) is, for example, 8.0,7.0,6.0,5.0,4.0,3.0,
2.0 etc., lower limit is, for example, 7.0,6.0,5.0,4.0,3.0,2.0,1.0 etc..In one embodiment, from carbamate
From the viewpoint of the productivity of (methyl) acrylate, the molecular weight distribution (Mw/Mn) of polyisocyanates (A) is preferably 1.0~
8.0。
Weight average molecular weight (Mw) and number-average molecular weight (Mn) can be used as through the poly- of gel permeation chromatography (GPC) measurement
Styrene scaled value finds out (the same below).
As long as desired effect can be obtained, to the ratio of the polyisocyanates (A) relative to 100 mass parts of compound group
It is not particularly limited.Relative to 100 mass parts of above compound group, the upper limit of the ratio of polyisocyanates (A) is, for example, 70,
60,50,40,30,25,20,10 mass parts etc., lower limit are, for example, 60,50,45,40,30,20,10,5 mass parts etc..At one
In embodiment, from the viewpoint of having both high rigidity, low crimpiness, high refractive index, relative to 100 mass of above compound group
The ratio of the polyisocyanates (A) of part is preferably 5~70 mass parts, further preferably 20~70 mass parts.
<(methyl) acrylate (B) containing hydroxyl, also referred to as (B) ingredient>
In the present invention, so-called " (methyl) acrylate containing hydroxyl " indicates there is hydroxyl and (methyl) acryloyl group
Compound.
Simple function (methyl) acrylate containing hydroxyl can be used alone, and two or more merging can also be used.
(methyl) acrylate containing hydroxyl is, for example, (methyl) glycerol acrylate (B-1) containing hydroxyl, contains hydroxyl
More (methyl) acrylate (B-2) of (poly-) pentaerythrite, more (methyl) acrylate of (poly-) trimethylolpropane containing hydroxyl
(B-3), the simple function containing hydroxyl (methyl) acrylate (B-4) etc..
((methyl) glycerol acrylate (B-1) containing hydroxyl)
(methyl) glycerol acrylate containing hydroxyl is such as structural formula (B-1) compound represented.
[changing 5]
(in formula, Rb1~Rb3Can be each independently hydrogen atom, (methyl) acryloyl group, alkyl, aryl or
[changing 6]
(in formula, b be 1 or more integer),
Rb1~Rb3At least one for hydrogen atom or
[changing 7]
(in formula, b be 1 or more integer), meanwhile, at least one be (methyl) acryloyl group).
(methyl) glycerol acrylate containing hydroxyl be, for example, 2- hydroxyl -3- phenoxy propyl (methyl) acrylate,
2- hydroxyl -3- (methyl) acryloxypropyl (methyl) acrylate, 2- hydroxy-3-methoxy propyl (methyl) acrylic acid
Ester, 1- hydroxyl -2- phenoxy propyl (methyl) acrylate, 1- hydroxyl -2- (methyl) acryloxypropyl (methyl) propylene
Acid esters, 1- hydroxyl -2- methoxy-propyl (methyl) acrylate, 2- hydroxyl -3- phenoxy propyl (methyl) acrylate are in oneself
Ester addition product etc..
(more (methyl) acrylate (B-2) of (poly-) pentaerythrite containing hydroxyl)
More (methyl) acrylate of (poly-) pentaerythrite containing hydroxyl such as structural formula (B-2) compound represented.
[changing 8]
(in formula, the integer that m is 0 or more, Rb4~Rb9Can be each independently hydrogen atom, (methyl) acryloyl group or
[changing 9]
(in formula, integer that b is 1 or more), in structural formula (B-2), from Rb4~Rb9At least one selected is hydrogen atom,
Or
[changing 10]
(in formula, integer that b is 1 or more), while at least one is (methyl) acryloyl group.In addition, Rb7And Rb8For each
Group can be different for structural unit).
" more (methyl) acrylate of (poly-) pentaerythrite " expression is " from more (methyl) acrylate of pentaerythrite in the present invention
With at least one selected in the group of more (methyl) the acrylate compositions of polypentaerythritol ".
In addition, so-called " group can be different for each structural unit ", indicate for example in structural formula (B-2), m is
When 2,
[changing 11]
Rb7AWith Rb7BIt can be different groups, Rb8AWith Rb8BIt can be different groups (the same below).
More (methyl) acrylate of pentaerythrite are, for example, pentaerythrite two (methyl) acrylate, three (first of pentaerythrite
Base) acrylate etc..
More (methyl) acrylate of polypentaerythritol are, for example, dipentaerythritol two (methyl) acrylate, dipentaerythritol
Three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, three seasons penta
Tetrol two (methyl) acrylate, tripentaerythritol three (methyl) acrylate, tripentaerythritol four (methyl) acrylate, three
Pentaerythrite five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol seven (methyl) acrylic acid
Ester etc..
(more (methyl) acrylate (B-3) of (poly-) trimethylolpropane containing hydroxyl)
More (methyl) acrylate of (poly-) trimethylolpropane containing hydroxyl such as structural formula (B-3) compound represented.
[changing 12]
(in formula, the integer that p is 0 or more, Rb10~Rb13For hydrogen atom, (methyl) acryloyl group or [change 13]
(in formula, b be 1 or more integer), from Rb10~Rb13At least one selected for hydrogen atom or
[changing 14]
(in formula, b be 1 or more integer), meanwhile, at least one be (methyl) acryloyl group.In addition, Rb12For each knot
Group can be different for structure unit).
In the present invention, " more (methyl) acrylate of (poly-) trimethylolpropane " expression is " from the more (first of trimethylolpropane
Base) acrylate and poly- trimethylolpropane more (methyl) acrylate composition group in at least one selected ".
More (methyl) acrylate of trimethylolpropane are, for example, trimethylolpropane two (methyl) acrylate etc..
Poly- more (methyl) acrylate of trimethylolpropane are, for example, double trimethylolpropane two (methyl) acrylate, double
Trimethylolpropane tris (methyl) acrylate, double trimethylolpropane four (methyl) acrylate etc..
(simple function (methyl) acrylate (B-4) containing hydroxyl)
Simple function (methyl) acrylate containing hydroxyl is such as structural formula (B-4) compound represented.
[changing 15]
(in formula, Rb14For hydrogen atom or methyl, Rb15For straight-chain alkyl-sub, branched alkylidene, cycloalkylidene or
[changing 16]
(in formula, Rb15aFor hydrogen atom or alkyl (such as methyl)),
Rb16For hydrogen atom or
[changing 17]
(in formula, b be 1 or more integer))
Structural formula (B-4) compound represented is, for example, straight chained alkyl (methyl) acrylate containing hydroxyl, contains hydroxyl
Straight chained alkyl (methyl) the acrylate caprolactones addition product of base, contains branched alkyl (methyl) acrylate containing hydroxyl
Branched alkyl (methyl) the acrylate caprolactones addition product of hydroxyl, contains naphthenic base (methyl) acrylate containing hydroxyl
Naphthenic base (methyl) the acrylate caprolactones addition product of hydroxyl, polyalkylene glycol mono (methyl) acrylate, polyalkylene
Glycol list (methyl) acrylate caprolactones addition product etc..
Straight chained alkyl (methyl) acrylate containing hydroxyl is, for example, 2- hydroxyethyl (methyl) acrylate, 3- hydroxyl
Base propyl (methyl) acrylate, 4- hydroxybutyl (methyl) acrylate etc..
Straight chained alkyl (methyl) acrylate caprolactones addition product containing hydroxyl is, for example, 3- hydroxypropyl (methyl) third
Olefin(e) acid ester caprolactones addition product, 2- hydroxyethyl (methyl) acrylate caprolactones addition product, 4- hydroxybutyl (methyl) propylene
Acid esters caprolactones addition product etc..
Branched alkyl (methyl) acrylate containing hydroxyl is, for example, 2- hydroxypropyl (methyl) acrylate, 2- hydroxyl
Base butyl (methyl) acrylate, 3- hydroxybutyl (methyl) acrylate etc..
Branched alkyl (methyl) acrylate caprolactones addition product containing hydroxyl is, for example, 2- hydroxypropyl (methyl) third
Olefin(e) acid ester caprolactones addition product, 2- hydroxybutyl (methyl) acrylate caprolactones addition product, 3- hydroxybutyl (methyl) propylene
Acid esters caprolactones addition product etc..
Naphthenic base (methyl) acrylate containing hydroxyl is, for example, (methyl) dihydroxypropyl cyclohexyl etc..
Naphthenic base (methyl) acrylate caprolactones addition product containing hydroxyl is, for example, (methyl) dihydroxypropyl hexamethylene
Ester caprolactones addition product etc..
Polyalkylene glycol mono (methyl) acrylate is, for example, polyethyleneglycol (methyl) acrylate, polypropylene glycol list
(methyl) acrylate etc..
Polyalkylene glycol mono (methyl) acrylate caprolactones addition product is, for example, polyethyleneglycol (methyl) acrylic acid
Ester caprolactones addition product, (methyl) acrylic acid 2- hydroxy methacrylates caprolactones addition product etc..
As long as desired effect can be obtained, the hydroxyl value of (methyl) acrylate (B) containing hydroxyl is not limited especially
System.The upper limit of the hydroxyl value of (methyl) acrylate (B) containing hydroxyl is, for example, 500,490,450,400,350,300,250,
200,150,100,80,75,70,65,60,55,50,45,40,35,30,25,20mgKOH/g etc., lower limit is, for example, 400,
350,300,250,200,150,100,80,70,65,60,55,50,45,40,35mgKOH/g etc..In one embodiment,
From the viewpoint of having both high rigidity, low crimpiness, high refractive index, the hydroxyl value of more (methyl) acrylate (B) of polypentaerythritol
Preferably 35~500mgKOH/g, more preferably 35~490mgKOH/g.
In the present invention, hydroxyl value refers to the calculated value obtained by following formula:
(hydroxyl value)=(potassium hydroxide molecular weight: 56.1) × 1000/ (hydroxyl equivalent)；
(hydroxyl equivalent)=(molecular weight of 1 molecule)/(hydroxyl value present in 1 molecule).
As long as desired effect can be obtained, (methyl) acrylic acid of (methyl) acrylate (B) containing hydroxyl is worked as
Amount is not particularly limited.The upper limit of (methyl) acrylic equivalent of (methyl) acrylate (B) containing hydroxyl is, for example, 500,
450,400,350,300,250,200,150,140,130,120,110g/eq etc., lower limit is, for example, 140,130,120,110,
100,99,95g/eq etc..In one embodiment, from the viewpoint of having both high rigidity, low crimpiness, high refractive index, contain
(methyl) acrylic equivalent for having more (methyl) acrylate (B) of hydroxyl is preferably 95~500g/eq, and further preferably 99
~150g/eq.
In the present invention, the molecular weight that " (methyl) acrylic equivalent " refers to every mole of (methyl) acryloyl group, passes through
Following formula is found out:
((methyl) acrylic equivalent)=(molecular weight of 1 molecule)/((methyl) acryloyl present in 1 molecule
Radix).
Relative to 100 mass parts of above compound group, the ratio of more (methyl) acrylate (B) containing hydroxyl it is upper
Limit e.g. 80,70,60,50,40,35 mass parts etc., lower limit is, for example, 70,60,55,50,40,30 mass parts etc..At one
In embodiment, from the viewpoint of having both high rigidity and high refractive index, relative to 100 mass parts of compound group, contain hydroxyl
The ratios of more (methyl) acrylate (B) be preferably 30~80 mass parts.
<neither (A) ingredient nor (B) ingredient compound, also referred to as other compounds>
When manufacturing above-mentioned carbamate (methyl) acrylate, can be used neither (A) ingredient nor (B) ingredient
Compound.That is, the compound neither (A) ingredient nor (B) ingredient can be contained in above compound group.
In one embodiment, relative to 100 mass % of above compound group, the ratio of other compounds is, for example: 0
~50 mass %, less than 40 mass %, less than 25 mass %, less than 10 mass %, less than 5 mass %, less than 1 mass %, small
In 0.1 mass %, less than 0.01 mass %, 0 mass % etc..
In one embodiment, relative to 100 moles of % of above compound group, the ratio of other compounds is, for example: 0
It is~50 moles of %, less than 40 moles %, less than 25 moles %, less than 10 moles %, less than 5 moles %, less than 1 mole %, small
In 0.1 mole of %, less than 0.01 mole %, 0 mole of % etc..
The manufacturing method of above-mentioned carbamate (methyl) acrylate can use well known method, can make (A) at
Divide and (B) ingredient is in solvent solvent-free or appropriate (toluene etc.), in the presence of catalyst appropriate (tin octoate etc.), with
Reaction temperature (60~90 DEG C etc.) appropriate is reacted.
<relative scale of each ingredient>
As long as desired effect can be obtained, to polyisocyanates (A) and (methyl) acrylate (B) containing hydroxyl
Mass ratio (polyisocyanates (A)/(methyl) acrylate (B) containing hydroxyl) be not particularly limited.Polyisocyanates
(A) with the mass ratio of (methyl) acrylate (B) containing hydroxyl (polyisocyanates (A)/(methyl) acrylic acid containing hydroxyl
Ester (B)) the upper limit be, for example, 2.5,2,1.9,1.5,1.0,0.9,0.5,0.4,0.3 etc., lower limit is, for example, 2,1.9,1.5,
1.0,0.9,0.5,0.4,0.3,0.25 etc..In one embodiment, from having both high rigidity, low crimpiness, high refractive index
From the point of view of viewpoint, the mass ratio (polyisocyanates (A)/contain of polyisocyanates (A) and (methyl) acrylate (B) containing hydroxyl
Have (methyl) acrylate (B) of hydroxyl) it is preferably 0.25~2.5.
The upper limit example of the mass ratio (other compound/polyisocyanates (A)) of other compounds and polyisocyanates (A)
In this way 10,9,7.5,5,2.5,1,0.5 etc., lower limit is, for example, 9,7.5,5,2.5,1,0.5,0 etc..In one embodiment,
The mass ratio (other compound/polyisocyanates (A)) of other compounds and polyisocyanates (A) are preferably 0~10.
Mass ratio (other chemical combination of other compounds and more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl
More (methyl) acrylate (B) of object/polypentaerythritol containing hydroxyl) the upper limit be, for example, 1,0.9,0.75,0.5,0.25,
0.1,0.05 etc., lower limit is, for example, 0.9,0.75,0.5,0.25,0.1,0.05,0 etc..In one embodiment, Qi Tahua
Close mass ratio (other compounds/poly- containing hydroxyl of object and more (methyl) acrylate (B) of the polypentaerythritol containing hydroxyl
More (methyl) acrylate (B) of pentaerythrite) it is preferably 0~1.
As long as desired effect can be obtained, to the hydroxyl and polyisocyanic acid of (methyl) acrylate (B) containing hydroxyl
The ratio between amount of substance of isocyanate group of ester (A) [(OH)/(NCO)] is not particularly limited.(methyl) third containing hydroxyl
The upper limit example of the ratio between the hydroxyl of olefin(e) acid ester (B) and the amount of substance of isocyanate group of polyisocyanates (A) [(OH)/(NCO)]
In this way 3.0,2.5,2.0,1.5,1.0 etc., lower limit is, for example, 2.4,2.0,1.5,1.0,0.95 etc..In one embodiment,
The hydroxyl of (methyl) acrylate (B) containing hydroxyl and the ratio between the amount of substance of isocyanate group of polyisocyanates (A)
[(OH)/(NCO)] is preferably 0.95~3.0.<physical property etc. of carbamate (methyl) acrylate>
The weight average molecular weight (Mw) of carbamate (methyl) acrylate is not particularly limited.Carbamate
The upper limit of the weight average molecular weight (Mw) of (methyl) acrylate is, for example, 80000,70000,60000,50000,40000,
30000,20000,10000,9000,8000,7000,6000,5000,4000,3000 etc., lower limit is, for example, 70000,
60000、 50000、40000、30000、20000、10000、9000、8000、7000、6000、5000、 4000、3000、
2000,1750,1700,1500 etc..In one embodiment, from the productivity of carbamate (methyl) acrylate and film
From the viewpoint of, the weight average molecular weight (Mw) of carbamate (methyl) acrylate is preferably 1500~80000, further
Preferably 1700~80000.
The number-average molecular weight (Mn) of carbamate (methyl) acrylate is not particularly limited.Carbamate (first
Base) acrylate number-average molecular weight (Mn) the upper limit be, for example, 80000,70000,60000,50000,40000,30000,
20000、12000、10000、9000、 8100、8000、7800、7000、6000、5600、5000、4000、3500、3100、
3001,3000,2900,2000 etc., lower limit is, for example, 70000,60000,50000,40000,30000,20000,12000,
10000、9000、8100、8000、7800、7000、6000、5600、 5000、4000、3500、3100、3001、3000、2900、
2000,1500,1200,1000 etc..In one embodiment, from the production of carbamate (methyl) acrylate and film
From the viewpoint of property, the number-average molecular weight (Mn) of above-mentioned carbamate (methyl) acrylate is preferably 1000~80000, into
One step is preferably 1200~80000.
The molecular weight distribution (Mw/Mn) of carbamate (methyl) acrylate is not particularly limited.Carbamate
The upper limit of the molecular weight distribution (Mw/Mn) of (methyl) acrylate is, for example, 8.0,7.0,6.0,5.0,4.0,3.0,2.0 etc., under
Limit is, for example, 8.0,7.0,6.0,5.0,4.0,3.0,2.0,1.2,1.0 etc..In one embodiment, from carbamate
From the viewpoint of the productivity of (methyl) acrylate and film, the molecular weight distribution of above-mentioned carbamate (methyl) acrylate
It (Mw/Mn) is preferably 1.0~8.0, further preferably 1.2~6.0.
As long as desired effect can be obtained, simultaneously to (methyl) acrylic equivalent of carbamate (methyl) acrylate
It is not particularly limited.The upper limit of (methyl) acrylic equivalent of carbamate (methyl) acrylate is, for example, 400,350,
300,290,150,140,130,120,110g/eq etc., lower limit is, for example, 390,350,300,290,140,130,120,110,
100g/eq etc..In one embodiment, from the viewpoint of having both high rigidity, low crimpiness, carbamate (methyl)
(methyl) acrylic equivalent of acrylate is preferably 100~400g/eq, further preferably 280~400g/eq.
[activity energy-line solidifying type resin composition, also referred to as composition]
The present invention provides the active energy ray-curable resin combination for containing above-mentioned carbamate (methyl) acrylate
Object.
As long as desired effect can be obtained, the content of carbamate (methyl) acrylate is limited there is no special
System.Relative to 100 mass parts of above-mentioned composition, the upper limit of the content of above-mentioned carbamate (methyl) acrylate is, for example,
100,90,80,70,60,51,50,40,36,35,31,30,29,20,15 mass parts etc., lower limit is, for example, 90,80,70,60,
51,50,40,36,35,31,30,29,20,15,10 mass parts etc..In one embodiment, from having both high rigidity, low curling
From the viewpoint of property, high refractive index, relative to 100 mass parts of above-mentioned composition, above-mentioned carbamate (methyl) acrylate
Content be preferably 10~100 mass parts or so.
<Photoepolymerizationinitiater initiater>
In one embodiment, above-mentioned activity energy-line solidifying type resin composition contains Photoepolymerizationinitiater initiater.Light is poly-
Closing initiator various well known Photoepolymerizationinitiater initiaters can be used alone, and two or more merging can also be used.In addition, light
Polymerization initiator is used in the case where carrying out ultraviolet curing, however, photopolymerization is drawn in the case where carrying out electronic beam curing
Hair agent is not required.
Photoepolymerizationinitiater initiater is, for example: 1- hydroxy-cyclohexyl-phenyl ketone, 2,2- dimethoxy -1,2- diphenylethane -
1- ketone, 1- cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -
2- hydroxy-2-methyl-1- propane-1- ketone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propane-1- ketone, 2,4,6-
Trimethylbenzoy-dipheny-phosphine oxide, 4- methyl benzophenone etc..
Relative to 100 mass parts of above-mentioned composition, the upper limit of the content of Photoepolymerizationinitiater initiater is, for example, 10,9,8,7,6,
5,4,3,2,1 mass parts etc., lower limit are, for example, 9,8,7,6,5,4,3,2,1,0.5,0 mass parts etc..In an embodiment
In, from the viewpoint of the reaction of (methyl) acryloyl group progress, relative to 100 mass parts of above-mentioned composition, photopolymerization causes
The content of agent is preferably 0~10 mass parts.
Relative to 100 mass parts of carbamate (methyl) acrylate, the upper limit of the content of Photoepolymerizationinitiater initiater is for example
It is 66.7,65,60,55,50,45,40,35,30,25,20,15,10,9,8,7,6,5,4,3,2,1 mass parts etc., lower limit example
65,60,55,50,45,40,35,30,25,20,15,10,9,8,7,6,5,4,3,2,1,0.5,0 mass parts in this way etc..?
In one embodiment, from the viewpoint of the reaction of (methyl) acryloyl group progress, relative to carbamate (methyl) third
100 mass parts of olefin(e) acid ester, the content of Photoepolymerizationinitiater initiater are preferably 0~30.0 mass parts or so.
<polymerizable monomer>
In one embodiment, above-mentioned activity energy-line solidifying type resin composition contains polymerizable monomer.Polymerism
Monomer various well known polymerizable monomers can be used alone, and two or more merging can also be used.
Polymerizable monomer is, for example: isobornyl (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, tetrahydro chaff
Base (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, ethoxy (alkylen oxide-modified or epoxy-modified) (methyl) third
Olefin(e) acid ester, hydroxypropyl (methyl) acrylate, 4- hydroxyl butyl (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, the moon
Gui Ji (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, 1,4- butanediol two (alkylen oxide-modified or epoxy-modified)
(methyl) acrylate, 1,6-HD two (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, tetraethylene glycol two
(alkylen oxide-modified or epoxy-modified) (methyl) acrylate, tripropylene glycol two (alkylen oxide-modified or epoxy-modified) (methyl) third
Olefin(e) acid ester, trimethylolpropane tris (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, three (alkylene oxide of pentaerythrite
It is modified or epoxy-modified) (methyl) acrylate, pentaerythrite four (alkylen oxide-modified or epoxy-modified) (methyl) acrylic acid
Ester, dipentaerythritol five (alkylen oxide-modified or epoxy-modified) (methyl) acrylate, dipentaerythritol six (it is alkylen oxide-modified or
It is epoxy-modified) (methyl) acrylate, tripentaerythritol eight (alkylen oxide-modified or epoxy-modified) (methyl) acrylate etc..
In the present invention, " (alkylen oxide-modified or epoxy-modified) (methyl) acrylate " refers to " selected from by (methyl)
At least one in the group of acrylate, alkylen oxide-modified (methyl) acrylate and epoxy-modified (methyl) acrylate composition
Kind ".
The content of polymerizable monomer is not particularly limited.Relative to 100 mass parts of composition, the content of polymerizable monomer
The upper limit be, for example, 85,80,75,70,65,60,55,50,45,40,36,35,30,25,20,19,15,14,10,5 mass parts
Deng lower limit is, for example, 85,80,75,70,65,60,55,50,45,40,36,35,30,25,20,19,15,14,10,5,0 matter
Measure part etc..In one embodiment, from the viewpoint of having both high rigidity, low crimpiness, high refractive index, relative to composition
100 mass parts, the content of polymerizable monomer are preferably 0~85 mass parts or so, further preferably 0~70 mass parts or so.
Relative to 100 mass parts of carbamate (methyl) acrylate, the upper limit of the content of polymerizable monomer is, for example,
567,550,500,450,400,350,300,250,200,150,100,50,25,10,5,1 mass parts etc., lower limit is, for example,
550,500,450,400,350,300,250,200,150,100,50,25,10,5,1,0 mass parts etc..In an embodiment party
In formula, from the viewpoint of having both high rigidity, low crimpiness, high refractive index, relative to carbamate (methyl) acrylate
100 mass parts, the content of polymerizable monomer are preferably 0~567 mass parts or so, and further preferably 0~300 mass parts are left
It is right.
<antistatic agent>
In one embodiment, antistatic agent can be contained in above-mentioned composition.Antistatic agent can be used alone, can also
Two or more merging to be used.
Antistatic agent is, for example: the anionic antistatic agents such as alkyl phosphate；The cationic antistatic agents such as quaternary ammonium salt；
The non-ionic antistatic agents such as polyoxyethylene alkyl ether；Use the antistatic agent of the alkali metal salts such as lithium, sodium, potassium；Ionic liquid class
Antistatic agent etc..
The content of antistatic agent is not particularly limited.Relative to 100 mass parts of composition, the content of antistatic agent it is upper
Limit e.g. 100,50,40,30,20,15,10,5 mass parts etc., lower limit is, for example, 50,25,20,15,10,5,2.5,0 mass
Part etc..In one embodiment, from the viewpoint of coating, relative to 100 mass parts of composition, the content of antistatic agent
Preferably 0~100 mass parts or so, further preferably 0~25 mass parts or so.
Relative to 100 mass parts of carbamate (methyl) acrylate, the upper limit of the content of antistatic agent is, for example,
500,100,50 mass parts etc., lower limit are, for example, 100,50,25,10,5,1,0.5,0 mass parts etc..In an embodiment
In, from the viewpoint of the coating and antistatic property for having both antistatic agent, relative to carbamate (methyl) acrylate
100 mass parts, the content of antistatic agent are preferably 0~500 mass parts or so, further preferably 0~100 mass parts or so.
<retarder thinner>
In one embodiment, above-mentioned composition contains retarder thinner.Retarder thinner can be by various well known dilutions
Solvent is used alone, and two or more merging can also be used.In addition, retarder thinner is not sent out irradiating ultraviolet light preferably
The solvent of raw reaction (polymerization), i.e. ultraviolet light non-reactive solvent.
Retarder thinner is, for example: methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, butyl acetate, second
Alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, diacetone alcohol, acetylacetone,2,4-pentanedione, toluene, dimethylbenzene, n-hexane, ring
Hexane, hexahydrotoluene, normal heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4- dioxanes, propylene glycol monomethyl ether,
Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate etc..
Relative to 100 mass parts of above-mentioned composition, the upper limit of the content of retarder thinner is, for example, 1900,1750,1500,
1250,1000,750,500,250,100,50,25 mass parts etc., lower limit is, for example, 1750,1500,1250,1000,750,
500,250,100,50,25,0 mass parts etc..In one embodiment, from the viewpoint of coating, relative to composition
100 mass parts, the content of retarder thinner are, for example, 0~1900 mass parts etc..
Relative to 100 mass parts of above-mentioned carbamate (methyl) acrylate, the upper limit of the content of retarder thinner is for example
It is 1900,1750,1500,1250,1000,750,500,250,100,50,25 mass parts etc., lower limit is, for example, 1750,
1500,1250,1000,750,500,250,100,50,25,0 mass parts etc..In one embodiment, from the sight of coating
From the point of view of point, relative to 100 mass parts of above-mentioned carbamate (methyl) acrylate, the content of retarder thinner is, for example, 0~
1900 mass parts etc..
<additive>
Above-mentioned activity energy-line solidifying type resin composition can containing except above-mentioned carbamate (methyl) acrylate,
Reagent other than Photoepolymerizationinitiater initiater, polymerizable monomer, antistatic agent, retarder thinner is as additive.
Additive is, for example: antioxidant, ultraviolet absorbing agent, light stabilizer, defoaming agent, surface conditioner, anti-pollution
Agent, pigment, metal oxide microparticle dispersion, organic fine particles dispersion etc..
In one embodiment, relative to 100 mass parts of composition, the content of additive is, for example: 0.05~50 matter
Measure part, less than 40 mass parts, less than 25 mass parts, less than 10 mass parts, less than 5 mass parts, less than 1 mass parts, less than 0.1 matter
Measure part, less than 0.01 mass parts, 0 mass parts etc..
In another embodiment, relative to 100 mass parts of carbamate (methyl) acrylate, additive contains
Amount is, for example: 0.05~333 mass parts, less than 300 mass parts, less than 200 mass parts, less than 100 mass parts, less than 50 matter
Amount part, less than 25 mass parts, less than 10 mass parts, less than 5 mass parts, less than 1 mass parts, less than 0.1 mass parts, be less than
0.01 mass parts, 0 mass parts etc..
Above-mentioned composition by by above-mentioned carbamate (methyl) acrylate and polymerization initiator as needed,
Polymerizable monomer, retarder thinner and additive etc. are obtained by mixing using various well known methods.
Above-mentioned activity energy-line solidifying type resin composition can be used as coating agent, film coating agent, plastic sheet coating
Agent etc. uses.Film is, for example, with coating agent: tri acetyl cellulose membrane (TAC film) coating agent, acrylic film coating agent, ring
Olefin resin film (COP film) coating agent etc..[solidfied material]
The present invention provides the solidfied material of above-mentioned activity energy-line solidifying type resin composition.Above-mentioned solidfied material is by above-mentioned
Activity energy-line solidifying type resin composition irradiation ultraviolet light, electron beam, radioactive ray isoreactivity energy line and obtain.
The active energy ray used in curing reaction is, for example, ultraviolet light and electron beam.The light source of ultraviolet light is, for example, to have
There is the ultraviolet lamp etc. of xenon lamp, high-pressure sodium lamp, metal halide lamp.In addition, the configuration of light quantity, light source, conveying speed etc.
It can according to need and be adjusted, using high-pressure sodium lamp, there is 80~160W/cm or so light quantity relative to every
Lamp, preferably be allowed to solidify with conveying speed 5~50m/ minutes or so.On the other hand, in the case where electron beam, have 10
In the electron beam accelerator of the acceleration voltage of~300kV or so, preferably it was allowed to solid with conveying speed 5~50m/ minutes or so
Change.
[film]
The present invention provides the film for containing above-mentioned solidfied material.Above-mentioned film is wanted using above-mentioned solidfied material and various basement membranes as being constituted
The article of element.
Various well known basement membranes can be used in basement membrane, e.g.: polycarbonate membrane, acrylic film (poly-methyl methacrylate
Ester film etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, tri acetyl cellulose membrane,
ABS film, AS film, norbornene resin film, cycloolefin film, polyvinyl alcohol film etc..The thickness of basement membrane is not particularly limited, preferably
It is 15~100 μm or so.
Various well known method manufactures can be used in above-mentioned film.Specifically, by above-mentioned active energy ray-curable resin
Composition is coated on at least single side of above-mentioned basement membrane, is dried as needed, and active energy ray is then irradiated.Separately
Outside, it can also be coated with resin combination of the present embodiment on the uncoated face of obtained basement membrane, be bonded on it
Then other basement membranes irradiate active energy ray, thus manufacture laminated film.These films all can serve as optical film use.
Coating method is, for example: metering bar coater coating, wire rod coating, dip coated (ワ イ ヤ ー バ ー applies work), Meyer stick apply
Cloth, airblade coating, intaglio plate coating, reversed intaglio plate coating, hectographic printing, flexible version printing (Off レ キ ソ printing), silk-screen printing
Method etc..
Coating weight is not particularly limited, and the quality after drying is preferably 0.1~30g/m2, more preferably 1~20g/m2。
Embodiment
Hereafter the present invention is concretely demonstrated by embodiment and comparative example.But in above-mentioned preferred embodiment
Explanation and following embodiment merely to citing purpose and provide, be not to be mentioned to limit the purpose of the present invention
For.Therefore, the scope of the present invention is neither limited by the embodiment specifically recorded in this specification, also not by having in this specification
The embodiment that body is recorded limits, and the scope of the present invention is only limited by the range of claims.Meanwhile as long as no especially saying
Bright, in each embodiment and comparative example, the numerical value of part, % etc. are quality criteria.
(weight average molecular weight)
Pass through gel permeation chromatography (Japanese Dong ソ ー (Co., Ltd.) manufacture, trade name " HLC-8220 "；Column: Japan east
ソ ー (Co., Ltd.) is manufactured, measured value obtained by trade name " TSKgel superHZM-M ".
Embodiment 1-1
The isocyanurate-modified of xylene diisocyanate is added in the reaction vessel for having agitating device, cooling tube
Object (タ ケ ネ ー ト D-131N Mitsui Chemicals (Co., Ltd.) manufacture) 300 parts of (225 parts of solid components), 0.6 part of tin octoate, 2-
After 240 parts of hydroxyl -3- phenoxypropylacrylate (エ Port キ シ エ ス テ Le M-600A, the manufacture of total chemistry society of Sakae society), warp
About 1 hour is spent, the temperature in system is warming up to about 80 DEG C.Then, after reaction system being kept 2 hours at the same temperature,
It is cooling, obtain urethane acrylate ((1) -1).Weight average molecular weight is 2900.Relative to 100 parts of the mixture, according to
Solid component ratio, cooperation 1- hydroxy-cyclohexyl-phenyl ketone (BASF Japan (Co., Ltd.) manufacture, trade name
" IRGACURE184 (イ Le ガ キ ュ ア ー 184) ", hereinafter referred to as HCPK) 5 parts, it is diluted, is made using methyl iso-butyl ketone (MIBK)
The activity energy-line solidifying type resin composition of standby nonvolatile component 40%.
For the embodiment and comparative example other than embodiment 1-1, in addition to by ingredient documented in table 1 change with
Outside, implementation is similarly operated with embodiment 1-1.
(manufacture of film)
In 100 μm of film thickness of PET films (eastern レ (Co., Ltd.) manufacture, trade name " Le ミ ラ ー 100U483 "), #14 is used
Rod coater is coated with each activity energy-line solidifying type resin composition, makes 7 μm of film thickness of the overlay film after solidifying, at 80 DEG C
It is 1 minute dry, manufacture film.Then obtained film is used into ultraviolet curing device (the manufacture name of an article: UBT-080-7A/BM, マ Le
チ プ ラ イ (Co., Ltd.) manufacture, high-pressure sodium lamp 600mJ/cm2), it is provided the film of curing overlay film.For the film of manufacture
Evaluation result is as shown in table 1 and table 2.
Hardness (pencil hardness)
According to JIS K5600-5-4, the hardness of solidfied material is evaluated by the pencil test of loading 500g.
Low crimpiness
The case where film is cut 10cm × 10cm, does not become tubular (situation that the end of film overlaps each other) according to film be
"○", as tubular the case where classify for "×".
Light resistance
In ultraviolet light self-discoloration instrument (trade name: ultraviolet light self-discoloration instrument U48AU, Japanese ス ガ testing machine (strain formula meeting
Society) manufacture) in, by film with carbon arc lamp exposure 100 hours.Film after test passes through colour difference meter (trade name: ZE 6000, Japan's electricity
Color industry (Co., Ltd.) manufacture) penetrant method be measured, if exposure after yellow colour index value (イ エ ロ ー イ Application デ ッ
Network ス value) less than 2, then it is classified as "○"；If being classified as "×" 2 or more.
Refractive index
It for film, is attached on the prism of Abbe refractometer by 1- bromonaphthalene, the refractive index (D of 589nm is carried out at 20 DEG C
Line) measurement.It is "○" if refractive index is 1.550 or more；If being classified as "×" less than 1.550.
[table 1]
[table 2]
[table 3]
Embodiment 2
When further being furtherd investigate for the activity energy-line solidifying type resin composition in present embodiment, discovery
The solidfied material (curing overlay film) of above-mentioned activity energy-line solidifying type resin composition has excellent antistatic property.
Synthesis example 1 (antistatic agent (4a))
It is added in the reaction vessel for having agitating device, cooling tube, dropping funel and nitrogen ingress pipe and contains quaternary ammonium salt
100 parts of methacryloxyethyl trimethyl ammonium chloride (hereinafter referred to as DMC), the 6-caprolactone 10mol of structure modified hydroxyl
60 parts of ethylmethyl acrylate, 40 parts of Tert-butyl Methacrylate (hereinafter referred to as t-BMA) and propylene glycol monomethyl ether
(PGME) 800 parts, 90 DEG C are warming up to.Then, 8 parts and 32 parts of PGME of 2,2 '-azo two (methylbutyronitrile) (AMBN) is added, opens
Beginning polymerization reaction, it is cooling after being kept for 6 hours at 100 DEG C, obtain the copolymer solution (nonvolatile component containing quaternary ammonium salt structure
20%) (" (4a) ingredient ").
Embodiment 2-1
Cooperate antistatic agent according to solid component ratio relative to 100 parts of urethane acrylate ((1) -1)
5 parts of (4a), 5 parts of HCPK, is diluted with PGME, prepares the active energy ray-curable resin combination of nonvolatile component 40%
Object.
Embodiment 2-2, comparative example 1-1
Other than changing ingredient documented in table 3, implementation is similarly operated with embodiment 2-1.
Antistatic property
For film, in polyester film (Japan's spinning (Co., Ltd.) manufacture, trade name " U ス モ シ ャ イ Application A- of 100 μ m-thicks
4100 ") on, the activity energy-line solidifying type resin composition (just preparation) of embodiment 1 is applied using #4 rod coater
Cloth (calculated value of film thickness: 2~3 μm), it is 1 minute dry at 80 DEG C.Then, obtained film is passed through into high pressure 2 times in air
Mercury lamp (200mJ/cm2), thus manufacture has the antistatic treatment optical film of cured film.For other embodiments and ratio
Activity energy-line solidifying type resin composition compared with example equally manufactures antistatic treatment optical film.Then, using commercially available resistance
Rate instrument (Mitsubishi Chemical (Co., Ltd.) manufacture, product name " Ha イ レ ス タ UP MCP-HT450 "), according to JIS K 6911,
Under applied voltage 500V, the sheet resistance of the solidfied material (cured film) of the film is measured.
[table 4]
Pentaerythritol triacrylate: ビ ス コ ー ト #260 (Osaka Organic Chemical Industry (strain))
2- hydroxyl -3- acryloxypropyl acrylate: the NK エ ス テ Le 701A (village Xin Zhong chemical industry
(strain))
Xylene diisocyanate biuret body: タ ケ ネ ー ト 114N (Mitsui Chemicals (strain))
Pentaerythritol tetraacrylate: ア ロ ニ ッ Network ス M-450 (East Asia synthesizes (strain)).
Claims (8)
1. carbamate (methyl) acrylate, carbamate (methyl) acrylate is containing following (A) and (B)
Compound group reaction product:
Polyisocyanates (A) is the polymer of xylene diisocyanate；And
(methyl) acrylate (B) containing hydroxyl.
2. carbamate (methyl) acrylate as described in claim 1, the polyisocyanates (A) is that dimethylbenzene two is different
Isocyanuric acid ester polymer, biuret polymer or the addition polymer of cyanate.
3. activity energy-line solidifying type resin composition, the activity energy-line solidifying type resin composition contains such as claim
Carbamate described in 1 or 2 (methyl) acrylate.
4. activity energy-line solidifying type resin composition as claimed in claim 3, the active energy ray-curable resin group
It closes object and contains Photoepolymerizationinitiater initiater.
5. activity energy-line solidifying type resin composition as described in claim 3 or 4, the active energy ray-curable resin
Composition contains polymerizable monomer.
6. such as the described in any item activity energy-line solidifying type resin compositions of claim 3~5, the active energy line curing
Type resin combination contains antistatic agent.
7. such as the solidfied material of the described in any item activity energy-line solidifying type resin compositions of claim 3~6.
8. containing the film of solidfied material as claimed in claim 7.
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| JP2017115556 | 2017-06-13 | ||
| JP2017-115556 | 2017-06-13 |
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| CN109134816A true CN109134816A (en) | 2019-01-04 |
| CN109134816B CN109134816B (en) | 2021-08-31 |
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| JP (1) | JP6885372B2 (en) |
| KR (1) | KR102314750B1 (en) |
| CN (1) | CN109134816B (en) |
| TW (1) | TWI736777B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239599A (en) * | 2019-07-16 | 2021-01-19 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102803332A (en) * | 2009-06-17 | 2012-11-28 | 日本化药株式会社 | Urethane (meth) acrylate compound and resin composition containing same |
| JP2014142555A (en) * | 2013-01-25 | 2014-08-07 | Dainippon Printing Co Ltd | Hard coat film, polarizing plate, and image display device |
| CN105143297A (en) * | 2013-04-26 | 2015-12-09 | 大赛璐湛新株式会社 | Urethane (meth)acrylate and active energy ray-curable resin composition |
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| JP3058751B2 (en) * | 1992-03-11 | 2000-07-04 | 日本化薬株式会社 | Resin composition, ultraviolet curable resin composition for transmission screen and cured product thereof |
| JP3676260B2 (en) * | 2000-12-28 | 2005-07-27 | ナトコ株式会社 | Active energy ray curable urethane (meth) acrylate, active energy ray curable composition and use thereof |
| KR101013149B1 (en) | 2008-07-11 | 2011-02-10 | 정원옥 | sticker and method for manufacturing thereof |
| JP5255464B2 (en) | 2009-01-27 | 2013-08-07 | 株式会社日本総合研究所 | CONFERENCE SUPPORT DEVICE, CONFERENCE SUPPORT METHOD, AND COMPUTER PROGRAM |
| JP6371728B2 (en) * | 2015-03-24 | 2018-08-08 | 三井化学株式会社 | Primer composition and laminate |
| JP6364393B2 (en) * | 2015-09-30 | 2018-07-25 | 富士フイルム株式会社 | Planographic printing plate dummy plate, manufacturing method thereof, and printing method using the same |
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2018
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- 2018-06-12 KR KR1020180067206A patent/KR102314750B1/en active IP Right Grant
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102803332A (en) * | 2009-06-17 | 2012-11-28 | 日本化药株式会社 | Urethane (meth) acrylate compound and resin composition containing same |
| JP2014142555A (en) * | 2013-01-25 | 2014-08-07 | Dainippon Printing Co Ltd | Hard coat film, polarizing plate, and image display device |
| CN105143297A (en) * | 2013-04-26 | 2015-12-09 | 大赛璐湛新株式会社 | Urethane (meth)acrylate and active energy ray-curable resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239599A (en) * | 2019-07-16 | 2021-01-19 | 荒川化学工业株式会社 | Active energy ray-curable resin composition, aqueous resin composition, coating agent composition, cured film, and film |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201902971A (en) | 2019-01-16 |
| JP2019002006A (en) | 2019-01-10 |
| KR20180135813A (en) | 2018-12-21 |
| TWI736777B (en) | 2021-08-21 |
| KR102314750B1 (en) | 2021-10-18 |
| CN109134816B (en) | 2021-08-31 |
| JP6885372B2 (en) | 2021-06-16 |
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