JP2019112630A - Antistatic agent for active-energy ray curable resin composition, active-energy ray curable resin composition, cured product and film - Google Patents
Antistatic agent for active-energy ray curable resin composition, active-energy ray curable resin composition, cured product and film Download PDFInfo
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- JP2019112630A JP2019112630A JP2018238055A JP2018238055A JP2019112630A JP 2019112630 A JP2019112630 A JP 2019112630A JP 2018238055 A JP2018238055 A JP 2018238055A JP 2018238055 A JP2018238055 A JP 2018238055A JP 2019112630 A JP2019112630 A JP 2019112630A
- Authority
- JP
- Japan
- Prior art keywords
- energy ray
- mass
- curable resin
- resin composition
- structural unit
- 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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- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 239000002216 antistatic agent Substances 0.000 title claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 63
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 47
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 150000002596 lactones Chemical class 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 9
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 9
- 238000007142 ring opening reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 35
- 229920000193 polymethacrylate Polymers 0.000 description 22
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000000654 additive Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 125000004185 ester group Chemical group 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
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- -1 acrylic compound Chemical class 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000463 material Substances 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
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 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
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- 239000003505 polymerization initiator Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000008096 xylene Substances 0.000 description 2
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- 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
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- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- 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
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- C08F218/04—Vinyl esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- 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
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- 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
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- 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
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- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/26—Use as polymer for film forming
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
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Abstract
Description
本開示は、活性エネルギー線硬化性樹脂組成物用帯電防止剤、活性エネルギー線硬化性樹脂組成物、硬化物及びフィルムに関する。 The present disclosure relates to an antistatic agent for an active energy ray curable resin composition, an active energy ray curable resin composition, a cured product, and a film.
活性エネルギー線硬化性樹脂組成物をフラットパネルディスプレイ用途に用いる場合、ディスプレイの組立や作動中の静電気に起因したトラブルを防止したり、高精細画像を実現したりするために、良好な帯電防止性が要求されるため、帯電防止剤が使用されている。 When the active energy ray-curable resin composition is used for flat panel display applications, it has good antistatic properties in order to prevent problems due to static electricity during assembly and operation of the display and to realize high definition images. Antistatic agents have been used because they are required.
帯電防止剤には、帯電防止性とともに透明性、耐擦傷性、及び耐湿熱性が良好であることが求められる。そこで、発明が解決しようとする課題は良好な帯電防止性を示し、かつ透明性、耐擦傷性、及び耐湿熱性も良好な帯電防止剤を提供することとする。 The antistatic agent is required to have good transparency, abrasion resistance, and heat and humidity resistance as well as antistatic properties. Therefore, the problem to be solved by the invention is to provide an antistatic agent which exhibits good antistatic properties and good transparency, scratch resistance, and moisture and heat resistance.
本発明者らは、鋭意検討した結果、特定のモノマーを用い、かつポリマーの分子量分布を特定の値に制御したポリマーを用いることにより、上記課題が解決されることを見出した。 As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific monomer and using a polymer in which the molecular weight distribution of the polymer is controlled to a specific value.
本開示により以下の項目が提供される。
（項目１）
四級アンモニウム塩構造を含むビニルモノマー由来の構成単位（ａ１）、
水酸基含有ビニルモノマーとラクトンとの開環重付加物であり、かつ、
重量平均分子量が１，０００〜１０，０００であるビニルモノマー由来の構成単位（ａ２）、
及び
炭素数３〜５の分岐アルキルエステル基を含むビニルモノマー由来の構成単位（ａ３）を含み、
分子量分布（Ｍｗ／Ｍｎ）が１．８〜５．０である、ポリマー（Ａ）を含む、
活性エネルギー線硬化性樹脂組成物用帯電防止剤。
（項目２）
上記項目に記載の活性エネルギー線硬化性樹脂組成物用帯電防止剤を含む、活性エネルギー線硬化性樹脂組成物。
（項目３）
上記項目に記載の活性エネルギー線硬化性樹脂組成物の硬化物。
（項目４）
上記項目に記載の硬化物を含む、フィルム。
The following items are provided by the present disclosure.
(Item 1)
Structural unit (a1) derived from a vinyl monomer containing quaternary ammonium salt structure,
A ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone, and
Component units (a2) derived from a vinyl monomer having a weight average molecular weight of 1,000 to 10,000,
And a structural unit (a3) derived from a vinyl monomer containing a branched alkyl ester group having 3 to 5 carbon atoms,
A polymer (A), having a molecular weight distribution (Mw / Mn) of 1.8 to 5.0,
Antistatic agent for active energy ray curable resin composition.
(Item 2)
The active energy ray curable resin composition containing the antistatic agent for active energy ray curable resin compositions as described in the said item.
(Item 3)
Hardened | cured material of the active energy ray curable resin composition as described in the said item.
(Item 4)
The film containing the hardened | cured material as described in the said item.
本開示において、上述した１又は複数の特徴は、明示された組み合わせに加え、さらに組み合わせて提供され得る。 In the present disclosure, one or more of the features described above may be provided in further combination in addition to the explicitly shown combination.
上記帯電防止剤は良好な帯電防止性、透明性、耐擦傷性、及び耐湿熱性を併せ持つという効果を奏する。 The above-mentioned antistatic agent exhibits an effect of having good antistatic property, transparency, abrasion resistance, and heat and humidity resistance.
本開示の全体にわたり、各物性値、含有量等の数値の範囲は、適宜（例えば下記の各項目に記載の上限及び下限の値から選択して）設定され得る。具体的には、数値αについて、数値αの上限及び下限としてＡ１、Ａ２、Ａ３、Ａ４（Ａ１＞Ａ２＞Ａ３＞Ａ４とする）等が例示される場合、数値αの範囲は、Ａ１以下、Ａ２以下、Ａ３以下、Ａ２以上、Ａ３以上、Ａ４以上、Ａ１〜Ａ２、Ａ１〜Ａ３、Ａ１〜Ａ４、Ａ２〜Ａ３、Ａ２〜Ａ４、Ａ３〜Ａ４等が例示される。 A range of numerical values such as each physical property value and the content may be appropriately set (for example, selected from the values of the upper limit and the lower limit described in each item below) throughout the present disclosure. Specifically, when the numerical value α is exemplified by A1, A2, A3, A4 (A1> A2> A3> A4) as the upper and lower limits of the numerical value α, the range of the numerical value α is A1 or less, A2 or less, A3 or less, A2 or more, A3 or more, A4 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, A3 to A4 and the like are exemplified.
[ポリマー（Ａ）]
本開示は、四級アンモニウム塩構造を含むビニルモノマー由来の構成単位（ａ１）、水酸基含有ビニルモノマーとラクトンとの開環重付加物であり、かつ、重量平均分子量が１，０００〜１０，０００であるビニルモノマー由来の構成単位（ａ２）、及び炭素数３〜５の分岐アルキルエステル基を含むビニルモノマー由来の構成単位（ａ３）を含み、分子量分布（Ｍｗ／Ｍｎ）が１．８〜５．０である、ポリマー（Ａ）を提供する。
[Polymer (A)]
The present disclosure is a constituent unit (a1) derived from a vinyl monomer containing a quaternary ammonium salt structure, a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone, and a weight average molecular weight of 1,000 to 10,000. And a structural unit (a3) derived from a vinyl monomer containing a branched alkyl ester group having 3 to 5 carbon atoms, and having a molecular weight distribution (Mw / Mn) of 1.8 to 5 Provided is a polymer (A) which is
＜四級アンモニウム塩構造を含むビニルモノマー由来の構成単位（ａ１）＞
四級アンモニウム塩構造を含むビニルモノマー由来の構成単位（ａ１）は、四級アンモニウム塩構造を含むビニルモノマー（ａ１’）を用いてポリマーを製造した際にポリマー鎖に含まれる構成単位である。上記ビニルモノマー（ａ１’）は２種以上を併用できる。
<Constituent unit derived from vinyl monomer containing quaternary ammonium salt structure (a1)>
The structural unit (a1) derived from a vinyl monomer containing a quaternary ammonium salt structure is a structural unit contained in a polymer chain when a polymer is produced using a vinyl monomer (a1 ′) containing a quaternary ammonium salt structure. The said vinyl monomer (a1 ') can use 2 or more types together.
四級アンモニウム塩構造を含むビニルモノマー（ａ１’）は、式（１）：
[ＣＨ２＝Ｃ（Ｒ１）−Ｃ（＝Ｏ）−Ａ−Ｂ−Ｎ＋（Ｒ２）（Ｒ３）（Ｒ４）]ｎ・Ｘｎ−
（式中、Ｒ１はＨ又はＣＨ３、Ｒ２〜Ｒ４は炭素数１〜３程度のアルキル基を、ＡはＯ又はＮＨを、Ｂは炭素数１〜３程度のアルキレン基を、Ｘ−はカウンターアニオン種を、ｎは１以上の整数を表す）で表わされる（メタ）アクリレート化合物等が例示される。また、Ｘ−は、Ｃｌ−、ＳＯ４ ２−、ＳＯ３ −、Ｃ２Ｈ５ＳＯ４ −、Ｂｒ−等が例示され、帯電防止効果の点よりＣｌ−が最も好ましい。なお、（ａ１）成分の市販品は、共栄社化学（株）製「ライトエステルＤＱ−１００」、興人（株）製「ＤＭＡＥＡ−Ｑ」等が例示される。
The vinyl monomer (a1 ′) containing a quaternary ammonium salt structure has the formula (1):
[CH 2 CC (R 1 ) -C (= O) -A-B-N + (R 2 ) (R 3 ) (R 4 )] n · X n −
(Wherein, R 1 is H or CH 3 , R 2 to R 4 is an alkyl group having about 1 to 3 carbon atoms, A is O or NH, B is an alkylene group having about 1 to 3 carbon atoms, And- represents a counter anion species, and n represents an integer of 1 or more. Further, X − is exemplified by Cl − , SO 4 2− , SO 3 − , C 2 H 5 SO 4 − , Br − and the like, and Cl − is most preferable in terms of the antistatic effect. Commercially available products of the component (a1) include “Light Ester DQ-100” manufactured by Kyoeisha Chemical Co., Ltd., “DMAEA-Q” manufactured by Kojin Co., and the like.
炭素数１〜３のアルキル基は、メチル基、エチル基、プロピル基、イソプロピル基が例示される。 Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group and an isopropyl group.
炭素数１〜３のアルキレン基は、メチレン基、エチレン基、プロピレン基、イソプロピレン基が例示される。 A methylene group, ethylene group, a propylene group, an isopropylene group is illustrated the C1-C3 alkylene group.
ポリマーの全質量に対する構成単位（ａ１）の含有量の上限及び下限は、６０、５５、５０、４５、４０、３５、３０質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位（ａ１）を３０〜６０質量％含むことが好ましい。 The upper limit and the lower limit of the content of the structural unit (a1) with respect to the total mass of the polymer are, for example, 60, 55, 50, 45, 40, 35, 30% by mass and the like. In one embodiment, it is preferable to contain 30-60 mass% of structural units (a1) with respect to the total mass of a polymer.
＜水酸基含有ビニルモノマーとラクトンとの開環重付加物であり、かつ、重量平均分子量が１，０００〜１０，０００であるビニルモノマー由来の構成単位（ａ２）＞
水酸基含有ビニルモノマーとラクトンとの開環重付加物であり、かつ、重量平均分子量が１，０００〜１０，０００であるビニルモノマー由来の構成単位（ａ２）とは、水酸基含有ビニルモノマーとラクトンとの開環重付加物であり、かつ、重量平均分子量が１，０００〜１０，０００であるビニルモノマー（ａ２’）を用いてポリマーを製造した際にポリマー鎖に含まれる構成単位である。上記ビニルモノマー（ａ２’）は２種以上を併用できる。
<A structural unit derived from a vinyl monomer which is a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone and has a weight average molecular weight of 1,000 to 10,000>
The structural unit (a2) derived from a vinyl monomer which is a ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone and has a weight average molecular weight of 1,000 to 10,000 is a hydroxyl group-containing vinyl monomer and a lactone And a structural unit included in a polymer chain when a polymer is produced using a vinyl monomer (a2 ′) having a weight average molecular weight of 1,000 to 10,000. The said vinyl monomer (a2 ') can use 2 or more types together.
上記ビニルモノマー（ａ２’）は、水酸基含有ビニルモノマーとラクトンとを用いて、公知の手法により開環重付加反応させることにより製造される。水酸基含有ビニルモノマーは２種以上を併用できるし、ラクトンも２種以上を併用できる。 The vinyl monomer (a2 ') is produced by a ring-opening polyaddition reaction using a hydroxyl group-containing vinyl monomer and a lactone according to a known method. The hydroxyl group-containing vinyl monomer can be used in combination of two or more, and lactone can also be used in combination of two or more.
水酸基含有ビニルモノマーは、水酸基含有（メタ）アクリル化合物、水酸基含有ビニルモノマー等が例示される。これらの中でも、特にラジカル共重合性の点より、水酸基含有（メタ）アクリル化合物が好ましい。 Examples of the hydroxyl group-containing vinyl monomer include a hydroxyl group-containing (meth) acrylic compound and a hydroxyl group-containing vinyl monomer. Among these, a hydroxyl group-containing (meth) acrylic compound is particularly preferable from the viewpoint of radical copolymerizability.
本開示において「（メタ）アクリレート」とは「アクリレート及びメタクリレートからなる群から選択される少なくとも１つ」を意味する。同様に「（メタ）アクリル」とは「アクリル及びメタクリルからなる群から選択される少なくとも１つ」を意味する。 In the present disclosure, “(meth) acrylate” means “at least one selected from the group consisting of acrylate and methacrylate”. Similarly, "(meth) acrylic" means "at least one selected from the group consisting of acrylic and methacrylic".
水酸基含有（メタ）アクリル化合物は、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート及びヒドロキシエチル（メタ）アクリルアミド等が例示される。 Examples of the hydroxyl group-containing (meth) acrylic compound include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and hydroxyethyl (meth) acrylamide.
水酸基含有ビニルモノマーは、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル及びヒドロキシジエチレングリコールビニルエーテル等が例示される。 Examples of hydroxyl group-containing vinyl monomers include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether and hydroxy diethylene glycol vinyl ether.
ラクトンは、β−プロピオラクトン、γ−ブチロラクトン、δ−バレロラクトン、β−メチル−δ−バレロラクトン及びε−カプロラクトン等が例示される。これらの中でも、特に開環重合の反応性の点より、ε−カプロラクトン及びδ−バレロラクトンからなる群から選ばれる１種が好ましい。 Examples of lactones include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone and ε-caprolactone. Among these, in particular, from the viewpoint of the reactivity of ring-opening polymerization, one selected from the group consisting of ε-caprolactone and δ-valerolactone is preferable.
ポリマーの全質量に対する構成単位（ａ２）の含有量の上限及び下限は、５０、４５、４０、３５、３０、２５、２０、１５質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位（ａ２）を１５〜５０質量％含むことが好ましい。 The upper limit and the lower limit of the content of the structural unit (a2) with respect to the total mass of the polymer are, for example, 50, 45, 40, 35, 30, 25, 20, 15% by mass and the like. In one embodiment, it is preferable to contain 15-50 mass% of structural unit (a2) with respect to the total mass of a polymer.
ビニルモノマー（ａ２’）の重量平均分子量の上限及び下限は、１０，０００、８，０００、７，０００、６，０００、５，０００、４，０００、３，９９９、３，０００、２，０００、１，０００等が例示される。１つの実施形態において、ビニルモノマー（ａ２’）の重量平均分子量の範囲は、１，０００〜１０，０００が好ましい。 The upper limit and the lower limit of the weight average molecular weight of the vinyl monomer (a2 ') are 10,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,999, 3,000, 2, 000, 1,000, etc. are illustrated. In one embodiment, the weight average molecular weight of the vinyl monomer (a2 ') is preferably in the range of 1,000 to 10,000.
（ａ２）成分の製造方法は、前記水酸基含有ビニルモノマーを開始剤として、前記ラクトンを開環重付加反応させる方法等が例示される。上記重量平均分子量は反応の際に両者の仕込み比率や、反応温度、触媒種、触媒量を適宜選択することによって調整され得る。 Examples of the method for producing the component (a2) include a method in which the lactone is subjected to a ring opening polyaddition reaction using the hydroxyl group-containing vinyl monomer as an initiator. The weight average molecular weight can be adjusted by appropriately selecting the preparation ratio of the two, the reaction temperature, the catalyst species and the amount of catalyst during the reaction.
反応の際には、触媒が使用され得る。触媒は、硫酸及びリン酸等の鉱酸；リチウム、ナトリウム及びカリウム等のアルカリ金属；ｎ−ブチルリチウム及びｔ−ブチルリチウム等のアルキル金属化合物；チタンテトラブトキシド等の金属アルコキシド；ジブチルスズジラウレート、ジブチルスズジオクテート、ジブチルスズメルカプチド及びオクチル酸スズ等のスズ化合物等が例示される。触媒の使用量は、水酸基含有ビニルモノマー及びラクトンの合計１００質量％に対して０．０１〜１０質量％程度が好ましい。 A catalyst may be used during the reaction. The catalyst includes mineral acids such as sulfuric acid and phosphoric acid; alkali metals such as lithium, sodium and potassium; alkyl metal compounds such as n-butyllithium and t-butyllithium; metal alkoxides such as titanium tetrabutoxide; dibutyltin dilaurate, dibutyltin geo Examples thereof include tin compounds such as cutate, dibutyltin mercaptide and tin octylate. The amount of the catalyst used is preferably about 0.01 to 10% by mass with respect to 100% by mass in total of the hydroxyl group-containing vinyl monomer and lactone.
＜炭素数３〜５の分岐アルキルエステル基を含むビニルモノマー由来の構成単位（ａ３）＞
炭素数３〜５の分岐アルキルエステル基を含むビニルモノマー由来の構成単位（ａ３）とは、炭素数３〜５の分岐アルキルエステル基を含むビニルモノマー（ａ３’）を用いてポリマーを製造した際にポリマー鎖に含まれる構成単位である。上記ビニルモノマー（ａ３’）は２種以上を併用できる。１つの実施形態において、上記ビニルモノマー（ａ３’）は脂環構造を有さない。この場合、構成単位（ａ３）は脂環構造を有さないものとなる。
<Constituent unit derived from vinyl monomer containing branched alkyl ester group having 3 to 5 carbon atoms (a3)>
When a polymer is produced using the vinyl monomer (a3 ') containing a C3-C5 branched alkyl ester group with the structural unit (a3) derived from the vinyl monomer containing a C3-C5 branched alkyl ester group Are structural units contained in the polymer chain. The said vinyl monomer (a3 ') can use 2 or more types together. In one embodiment, the vinyl monomer (a3 ') has no alicyclic structure. In this case, the structural unit (a3) does not have an alicyclic structure.
炭素数３〜５の分岐アルキルエステル基は、イソプロピルエステル基、イソブチルエステル基、ｓｅｃ−ブチルエステル基、ｔｅｒｔ−ブチルエステル基、１−メチルブチルエステル基、２−メチルブチルエステル基、３−メチルブチルエステル基、１−エチルプロピルエステル基、１，１−ジメチルプロピルエステル基、１，２−ジメチルプロピルエステル基、２，２−ジメチルプロピルエステル基が例示される。 The branched alkyl ester group having 3 to 5 carbon atoms is an isopropyl ester group, an isobutyl ester group, a sec-butyl ester group, a tert-butyl ester group, a 1-methylbutyl ester group, a 2-methylbutyl ester group, 3-methylbutyl Examples thereof include an ester group, 1-ethylpropyl ester group, 1,1-dimethylpropyl ester group, 1,2-dimethylpropyl ester group and 2,2-dimethylpropyl ester group.
炭素数３〜５の分岐アルキルエステル基を含むビニルモノマー（ａ３’）は、イソプロピル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート及びイソペンチル（メタ）アクリレート等が例示される。 Examples of the vinyl monomer (a3 ') containing a branched alkyl ester group having 3 to 5 carbon atoms include isopropyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate and isopentyl (meth) acrylate, etc. .
ポリマーの全質量に対する構成単位（ａ３）の含有量の上限及び下限は、４０、３５、３０、２５、２０、１５、１０、５質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位（ａ３）を５〜４０質量％含むことが好ましい。 The upper limit and the lower limit of the content of the structural unit (a3) with respect to the total mass of the polymer are 40, 35, 30, 25, 25, 20, 15, 10, 5% by mass and the like. In one embodiment, it is preferable to contain 5-40 mass% of structural units (a3) with respect to the total mass of a polymer.
＜構成単位（ａ１）〜（ａ３）以外の構成単位（ａ４）＞
上記ポリマーには、上記構成単位（ａ１）〜（ａ３）以外の構成単位（ａ４）（「その他の構成単位（ａ４）」ともいう）を含んでいてもよい。その他の構成単位（ａ４）は、上記モノマー（ａ１’）〜（ａ３’）以外のモノマー（「その他のモノマー」、「モノマー（ａ４’）」ともいう）を用いてポリマーを製造した際にポリマー鎖に含まれる構成単位である。その他のモノマーは２種以上を併用できる。
<Structural units other than the structural units (a1) to (a3) (a4)>
The polymer may contain a structural unit (a4) (also referred to as “other structural unit (a4)”) other than the structural units (a1) to (a3). The other structural unit (a4) is a polymer when a polymer is produced using monomers other than the above monomers (a1 ′) to (a3 ′) (also referred to as “other monomers” and “monomer (a4 ′)”) It is a structural unit contained in a chain. Other monomers can be used in combination of two or more.
モノマー（ａ４’）は、（ａ３）成分に該当しないモノ（メタ）アクリレート、芳香環構造含有ビニルモノマー等が例示される。 Examples of the monomer (a4 ') include mono (meth) acrylates and aromatic ring structure-containing vinyl monomers which do not correspond to the component (a3).
（ａ３）成分に該当しないモノ（メタ）アクリレートは、炭素数１〜１０程度の炭化水素基を有するモノ（メタ）アクリレート等が例示される。 Examples of the mono (meth) acrylate which does not correspond to the component (a3) include mono (meth) acrylate having a hydrocarbon group having about 1 to 10 carbon atoms.
上記炭素数１〜１０程度の炭化水素基を有するモノ（メタ）アクリレートは、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート及びフェニル（メタ）アクリレート等が例示される。 The mono (meth) acrylate having a hydrocarbon group having about 1 to 10 carbon atoms is methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, hexyl Examples include meta) acrylates, benzyl (meth) acrylates and phenyl (meth) acrylates.
上記芳香環構造含有ビニルモノマーは、スチレン、α−メチルスチレン及び４−メチルスチレン等が例示される。 Examples of the aromatic ring structure-containing vinyl monomer include styrene, α-methylstyrene and 4-methylstyrene.
ポリマーの全質量に対する構成単位（ａ４）の含有量の上限及び下限は、５０、４５、４０、３５、３０、２５、２０、１５、１０、５、１、０質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位（ａ４）を０〜５０質量％含むことが好ましい。 The upper limit and the lower limit of the content of the structural unit (a4) with respect to the total mass of the polymer are, for example, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1 and 0% by mass. In one embodiment, it is preferable to include the structural unit (a4) in an amount of 0 to 50% by mass based on the total mass of the polymer.
＜構成単位間の相対比＞
構成単位（ａ１）と構成単位（ａ２）との質量比（構成単位（ａ１）の質量／構成単位（ａ２）の質量）の上限及び下限は、４、３．５、３、２．５、２、１．５、１、０．５等が例示される。１つの実施形態において、構成単位（ａ１）と構成単位（ａ２）との質量比（構成単位（ａ１）の質量／構成単位（ａ２）の質量）は０．５〜４が好ましい。
<Relative ratio between building blocks>
The upper and lower limits of the mass ratio of the structural unit (a1) to the structural unit (a2) (mass of structural unit (a1) / mass of structural unit (a2)) are 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, etc. are illustrated. In one embodiment, the mass ratio of the structural unit (a1) to the structural unit (a2) (the mass of the structural unit (a1) / the mass of the structural unit (a2)) is preferably 0.5 to 4.
構成単位（ａ１）と構成単位（ａ３）との質量比（構成単位（ａ１）の質量／構成単位（ａ３）の質量）の上限及び下限は、１２、１１、１０、９、７．５、５、２．５、１、０．５等が例示される。１つの実施形態において、構成単位（ａ１）と構成単位（ａ３）との質量比（構成単位（ａ１）の質量／構成単位（ａ３）の質量）は０．５〜１２が好ましい。 The upper limit and the lower limit of the mass ratio of the structural unit (a1) to the structural unit (a3) (mass of structural unit (a1) / mass of structural unit (a3)) are 12, 11, 10, 9, 7.5, 5, 2.5, 1, 0.5, etc. are illustrated. In one embodiment, the mass ratio of the structural unit (a1) to the structural unit (a3) (mass of structural unit (a1) / mass of structural unit (a3)) is preferably 0.5 to 12.
構成単位（ａ２）と構成単位（ａ３）との質量比（構成単位（ａ２）の質量／構成単位（ａ３）の質量）の上限及び下限は、１０、９、７．５、５、２．５、１、０．５、０．３等が例示される。１つの実施形態において、構成単位（ａ２）と構成単位（ａ３）との質量比（構成単位（ａ２）の質量／構成単位（ａ３）の質量）は０．３〜１０が好ましい。 The upper limit and the lower limit of the mass ratio of the structural unit (a2) to the structural unit (a3) (the mass of the structural unit (a2) / the mass of the structural unit (a3)) are 10, 9, 7.5, 5, 2. 5, 1, 0.5, 0.3, etc. are illustrated. In one embodiment, the mass ratio of the structural unit (a2) to the structural unit (a3) (the mass of the structural unit (a2) / the mass of the structural unit (a3)) is preferably 0.3 to 10.
構成単位（ａ４）と構成単位（ａ１）との質量比（構成単位（ａ４）の質量／構成単位（ａ１）の質量）の上限及び下限は、２、１．５、１、０．５、０．１、０等が例示される。１つの実施形態において、構成単位（ａ４）と構成単位（ａ１）との質量比（構成単位（ａ４）の質量／構成単位（ａ１）の質量）は０〜２が好ましい。 The upper limit and the lower limit of the mass ratio of the structural unit (a4) to the structural unit (a1) (the mass of the structural unit (a4) / the mass of the structural unit (a1)) are 2, 1.5, 1, 0.5, 0.1, 0 etc. are illustrated. In one embodiment, the mass ratio of the structural unit (a4) to the structural unit (a1) (mass of structural unit (a4) / mass of structural unit (a1)) is preferably 0-2.
構成単位（ａ４）と構成単位（ａ２）との質量比（構成単位（ａ４）の質量／構成単位（ａ２）の質量）の上限及び下限は、４、３、２、１、０．５、０．１、０等が例示される。１つの実施形態において、構成単位（ａ４）と構成単位（ａ２）との質量比（構成単位（ａ４）の質量／構成単位（ａ２）の質量）は０〜４が好ましい。 The upper limit and lower limit of the mass ratio of the structural unit (a4) to the structural unit (a2) (mass of structural unit (a4) / mass of structural unit (a2)) are 4, 3, 2, 1, 0.5, 0.1, 0 etc. are illustrated. In one embodiment, the mass ratio of the structural unit (a4) to the structural unit (a2) (mass of structural unit (a4) / mass of structural unit (a2)) is preferably 0 to 4.
構成単位（ａ４）と構成単位（ａ３）との質量比（構成単位（ａ４）の質量／構成単位（ａ３）の質量）の上限及び下限は、１０、９、７．５、５、４、３、２、１、０．５、０．１、０等が例示される。１つの実施形態において、構成単位（ａ４）と構成単位（ａ３）との質量比（構成単位（ａ４）の質量／構成単位（ａ３）の質量）は０〜１０が好ましい。 The upper limit and the lower limit of the mass ratio of the structural unit (a4) to the structural unit (a3) (mass of structural unit (a4) / mass of structural unit (a3)) are 10, 9, 7.5, 5, 4, 3, 2, 1, 0.5, 0.1, 0 etc. are illustrated. In one embodiment, the mass ratio of the structural unit (a4) to the structural unit (a3) (mass of structural unit (a4) / mass of structural unit (a3)) is preferably 0 to 10.
＜ポリマー（Ａ）の物性等＞
ポリマー（Ａ）の重量平均分子量（Ｍｗ）の上限及び下限は、５００，０００、４５０，０００、４００，０００、３５０，０００、３００，０００、２５０，０００、２００，０００、１８０，０００等が例示される。１つの実施形態において、ポリマー（Ａ）の重量平均分子量（Ｍｗ）は１８０，０００〜５００，０００が好ましい。
<Physical Properties of Polymer (A)>
The upper and lower limits of the weight-average molecular weight (Mw) of the polymer (A) are 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 180,000, etc. It is illustrated. In one embodiment, the weight average molecular weight (Mw) of the polymer (A) is preferably 180,000 to 500,000.
ポリマー（Ａ）の数平均分子量（Ｍｎ）の上限及び下限は、２００，０００、１７５，０００、１５０，０００、１００，０００、７５，０００、５０，０００等が例示される。１つの実施形態において、ポリマー（Ａ）の数平均分子量（Ｍｎ）は５０，０００〜２００，０００が好ましい。 The upper and lower limits of the number average molecular weight (Mn) of the polymer (A) are, for example, 200,000, 175,000, 150,000, 100,000, 75,000, 50,000 and the like. In one embodiment, the number average molecular weight (Mn) of the polymer (A) is preferably 50,000 to 200,000.
ポリマー（Ａ）の分子量分布（Ｍｗ／Ｍｎ）の上限及び下限は、５．０、４．９、４．５、４．０、３．５、３．０、２．５、２．０、１．９、１．８等が例示される。１つの実施形態において、ポリマー（Ａ）の分子量分布（Ｍｗ／Ｍｎ）は１．８〜５．０が好ましい。 The upper limit and the lower limit of the molecular weight distribution (Mw / Mn) of the polymer (A) are 5.0, 4.9, 4.5, 4.0, 3.5, 3.0, 2.5, 2.0, 1.9, 1.8, etc. are illustrated. In one embodiment, the molecular weight distribution (Mw / Mn) of the polymer (A) is preferably 1.8 to 5.0.
＜ポリマー（Ａ）の製造方法＞
（Ａ）成分は、モノマー（ａ１’）〜（ａ３’）、及び必要に応じてモノマー（ａ４’）成分を各種公知の方法（塊状重合、溶液重合、乳化重合等）でラジカル共重合させることにより得られる。反応時間は２〜１２時間程度が好ましい。なお、分子量分布は、重合温度や重合開始剤量により調整され得る。
<Method of producing polymer (A)>
Component (A) is obtained by radical copolymerization of monomers (a1 ′) to (a3 ′) and, if necessary, monomer (a4 ′) components by various known methods (mass polymerization, solution polymerization, emulsion polymerization, etc.) Obtained by The reaction time is preferably about 2 to 12 hours. The molecular weight distribution may be adjusted by the polymerization temperature or the amount of the polymerization initiator.
重合温度の上限及び下限は、１３０、１２０、１１０、１００、９０、８０、７５、７０℃等が例示される。１つの実施形態において、重合温度は７０〜１３０℃程度が好ましい。 The upper and lower limits of the polymerization temperature are, for example, 130, 120, 110, 100, 90, 80, 75, 70 ° C and the like. In one embodiment, the polymerization temperature is preferably about 70 to 130 ° C.
反応の際には、ラジカル重合開始剤を使用してもよい。ラジカル重合開始剤は、過酸化水素、過硫酸アンモニウム及び過硫酸カリウム等の無機過酸化物；ベンゾイルパーオキサイド、ジクミルパーオキサイド及びラウリルパーオキサイド等の有機過酸化物；２，２−アゾビス（イソブチロニトリル）及び２，２’−アゾビス（メチルブチロニトリル）等のアゾ系化合物等が例示される。ラジカル重合開始剤を使用する場合、その使用量は、モノマー（ａ１’）〜（ａ３’）、及びその他のモノマーの総質量に対し、０．０１〜１０質量％程度が好ましい。 At the time of reaction, a radical polymerization initiator may be used. Radical polymerization initiators include inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate; organic peroxides such as benzoyl peroxide, dicumyl peroxide and lauryl peroxide; 2, 2-azobis (isobutyl) Examples include azo compounds such as ronitrile) and 2,2'-azobis (methylbutyronitrile). When a radical polymerization initiator is used, its use amount is preferably about 0.01 to 10% by mass with respect to the total mass of the monomers (a1 ') to (a3') and other monomers.
また、反応の際に連鎖移動剤を使用してもよい。連鎖移動剤は、ドデシルメルカプタン、２−メルカプトベンゾチアゾール及びブロムトリクロロメタン等が例示される。連鎖移動剤を使用する場合、その使用量は、モノマー（ａ１’）〜（ａ３’）、及びその他のモノマーの総質量に対し、０．０１〜１０質量％程度が好ましい。 In addition, a chain transfer agent may be used in the reaction. Examples of chain transfer agents include dodecyl mercaptan, 2-mercaptobenzothiazole and bromotrichloromethane. When a chain transfer agent is used, its amount is preferably about 0.01 to 10% by mass with respect to the total mass of the monomers (a1 ') to (a3') and other monomers.
また、溶液重合の場合には、エチレングリコールモノエチルエーテル及びプロピレングリコールモノメチルエーテル等のグリコールエーテル溶剤；メタノール、エタノール及びｎ−プロパノール等のアルコール溶剤；メチルエチルケトン及びメチルイソブチルケトン等のケトン溶剤；ベンセン、トルエン及びキシレン等の芳香族炭化水素溶剤；酢酸エチル、酢酸ブチル等の酢酸エステル溶剤；クロロホルム及びジメチルホルムアミド等の有機溶剤を使用できる。これらの中でも（ａ１）成分〜（ａ４）成分の溶解力の点よりグリコールエーテル溶剤とアルコール溶剤が好ましい。また、乳化重合の場合には、各種公知のアニオン性、ノニオン性、カチオン性の界面活性剤を使用できる。 In the case of solution polymerization, glycol ether solvents such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether; alcohol solvents such as methanol, ethanol and n-propanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; bencene, toluene And aromatic hydrocarbon solvents such as xylene; acetic acid ester solvents such as ethyl acetate and butyl acetate; organic solvents such as chloroform and dimethylformamide. Among these, glycol ether solvents and alcohol solvents are preferable from the viewpoint of the solvency of the components (a1) to (a4). In the case of emulsion polymerization, various known anionic, nonionic and cationic surfactants can be used.
[活性エネルギー線硬化性樹脂組成物用帯電防止剤：「帯電防止剤」ともいう]
本開示は、上記ポリマー（Ａ）を含む、活性エネルギー線硬化性樹脂組成物用帯電防止剤を提供する。
[Antistatic agent for active energy ray curable resin composition: also referred to as "antistatic agent"]
The present disclosure provides an antistatic agent for an active energy ray-curable resin composition, which contains the polymer (A).
（希釈溶剤）
１つの実施形態において、上記帯電防止剤には希釈溶剤が含まれる。希釈溶剤は２種以上を併用してもよい。希釈溶剤は、メチルエチルケトン、メチルイソブチルケトン、酢酸メチル、酢酸エチル、酢酸ブチル、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブタノール、イソブチルアルコール、ｔｅｒｔ−ブチルアルコール、ジアセトンアルコール、アセチルアセトン、トルエン、キシレン、ｎ−ヘキサン、シクロヘキサン、メチルシクロヘキサン、ｎ−ヘプタン、イソプロピルエーテル、メチルセロソルブ、エチルセロソルブ、１，４−ジオキサン、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等が例示される。
(Dilution solvent)
In one embodiment, the antistatic agent comprises a diluent. The dilution solvent may be used in combination of two or more. Dilution solvents are methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol, acetylacetone, toluene, xylene , N-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. Ru.
希釈溶剤含有量は、特に制限されない。帯電防止剤１００質量部に対する希釈溶剤含有量の上限及び下限は、１９００、１５００、１０００、５００、１００、５０、２５、０質量部等が例示される。帯電防止剤中に希釈溶剤を含む場合、１つの実施形態において、希釈溶剤を帯電防止剤１００質量部に対し、塗工性の観点から、２５〜１９００質量部程度含むことが好ましい。 The dilution solvent content is not particularly limited. The upper limit and the lower limit of the dilution solvent content with respect to 100 parts by mass of the antistatic agent are, for example, 1900, 1500, 1000, 500, 100, 50, 25, 0, and 0 parts by mass. When the diluting agent is contained in the antistatic agent, in one embodiment, the diluting solvent is preferably contained in an amount of about 25 to 1900 parts by mass from the viewpoint of coatability with respect to 100 parts by mass of the antistatic agent.
（添加剤）
上記帯電防止剤は、上記ポリマー（Ａ）でも、希釈溶剤でもない剤を添加剤として含み得る。添加剤は２種以上を併用してもよい。添加剤は、酸化防止剤、紫外線吸収剤、光安定剤、消泡剤、表面調整剤、防汚染剤、顔料、金属酸化物微粒子分散体、有機微粒子分散体等が例示される。
(Additive)
The antistatic agent may contain, as an additive, an agent which is neither the polymer (A) nor a diluting solvent. The additives may be used in combination of two or more. Examples of the additive include an antioxidant, an ultraviolet light absorber, a light stabilizer, an antifoamer, a surface control agent, a pollution control agent, a pigment, a metal oxide particle dispersion, and an organic particle dispersion.
１つの実施形態において、添加剤含有量は、帯電防止剤固形分１００質量部に対して、０〜５０質量部、４０質量部未満、２５質量部未満、１０質量部未満、５質量部未満、１質量部未満、０．１質量部未満、０．０１質量部未満、０質量部等が例示される。 In one embodiment, the additive content is 0 to 50 parts by mass, less than 40 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass with respect to 100 parts by mass of the antistatic agent solid content. Less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass and the like are exemplified.
別の実施形態において、添加剤含有量は、ポリマー（Ａ）１００質量部に対して、０〜３３３質量部、３００質量部未満、２００質量部未満、１００質量部未満、５０質量部未満、２５質量部未満、１０質量部未満、５質量部未満、１質量部未満、０．１質量部未満、０．０１質量部未満、０質量部等が例示される。 In another embodiment, the additive content is 0 to 333 parts by mass, less than 300 parts by mass, less than 200 parts by mass, less than 100 parts by mass, less than 50 parts by mass, 25 parts by mass with respect to 100 parts by mass of the polymer (A). Less than 10 parts by weight, less than 5 parts by weight, less than 1 part by weight, less than 0.1 parts by weight, less than 0.01 parts by weight, 0 parts by weight and the like are exemplified.
[活性エネルギー線硬化性樹脂組成物：「組成物」ともいう]
本開示は、上記活性エネルギー線硬化性樹脂組成物用帯電防止剤を含む、活性エネルギー線硬化性樹脂組成物を提供する。上記活性エネルギー線硬化性樹脂組成物は、上記活性エネルギー線硬化性樹脂組成物用帯電防止剤以外に、５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレート、反応性希釈剤、光重合開始剤、及び／又は添加剤を含み得る。
[Active energy ray curable resin composition: also referred to as “composition”]
The present disclosure provides an active energy ray-curable resin composition that includes the above-described antistatic agent for an active energy ray-curable resin composition. The said active energy ray curable resin composition is poly (meth) acrylate which has five or more (meth) acryloyl groups other than the said antistatic agent for active energy ray curable resin compositions, a reactive diluent, light It may contain a polymerization initiator and / or an additive.
（５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレート）
５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートは、非ウレタン変性ポリ（メタ）アクリレート（１）（（１）成分ともいう）、ウレタン変性ポリ（メタ）アクリレート（２）（（２）成分ともいう）等が例示される。５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートは２種以上を併用してもよい。
(Poly (meth) acrylate having 5 or more (meth) acryloyl groups)
The poly (meth) acrylate having five or more (meth) acryloyl groups is a non-urethane modified poly (meth) acrylate (1) (also referred to as component (1)), a urethane modified poly (meth) acrylate (2) 2) It is also referred to as a component) etc. Two or more kinds of poly (meth) acrylates having five or more (meth) acryloyl groups may be used in combination.
非ウレタン変性ポリ（メタ）アクリレート（１）は、ジペンタエリスリトールポリ（メタ）アクリレート、トリペンタエリスリトールポリ（メタ）アクリレート及びポリペンタエリスリトールポリ（メタ）アクリレート等が例示される。 Examples of non-urethane-modified poly (meth) acrylates (1) include dipentaerythritol poly (meth) acrylate, tripentaerythritol poly (meth) acrylate and polypentaerythritol poly (meth) acrylate.
ウレタン変性ポリ（メタ）アクリレート（２）は、上記（１）成分のうち１個以上の水酸基を有する成分もしくは４個以下の（メタ）アクリロイル基を有する水酸基含有（メタ）アクリレートと各種公知のポリイソシアネートとの化合物等が例示される。 The urethane-modified poly (meth) acrylate (2) is a component having one or more hydroxyl groups in the component (1) or a hydroxyl group-containing (meth) acrylate having 4 or less (meth) acryloyl groups and various known poly The compound etc. with an isocyanate are illustrated.
ポリイソシアネートは、芳香族ジイソシアネート、脂環族ジイソシアネート、及び脂肪族ジイソシアネート並びにこれらの多量体（２〜２０量体）等が例示される。これらの中でも硬化皮膜の耐候性の観点より脂環族ジイソシアネート化合物が好ましい。 Examples of the polyisocyanate include aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates, and multimers (2 to 20 monomers) of these. Among these, alicyclic diisocyanate compounds are preferable from the viewpoint of the weather resistance of the cured film.
芳香族ジイソシアネートは、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、１，３−キシレンジイソシアネート、ジフェニルメタン−４，４’−ジイソシアネート、３−メチル−ジフェニルメタンジイソシアネート及び１，５−ナフタレンジイソシアネート等が例示される。 Aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyl-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate Etc. are illustrated.
脂環族ジイソシアネートは、ジシクロヘキシルメタンジイソシアネート及びイソホロンジイソシアネート、水添キシレンジイソシアネート、水添トルエンジイソシアネート等が例示される。 Examples of alicyclic diisocyanates include dicyclohexylmethane diisocyanate and isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate and the like.
脂肪族ジイソシアネートは、ヘキサメチレンジイソシアネート等が例示される。 Examples of aliphatic diisocyanates include hexamethylene diisocyanate and the like.
５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートの分子量の上限及び下限は、１００００、９０００、８０００、７０００、５０００、４０００、３０００、２０００、１０００、９００、７５０、７００、６００、５５０が例示される。１つの実施形態において、５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートの分子量は、ポリマー（Ａ）との相溶性、硬化皮膜の帯電防止性、透明性、硬度、及び耐擦傷性等の観点から、５５０〜１００００程度が好ましく、５５０〜７０００程度がより好ましい。 The upper and lower limits of the molecular weight of the poly (meth) acrylate having five or more (meth) acryloyl groups are 10000, 9000, 8000, 7000, 5000, 4000, 3000, 2000, 1000, 900, 750, 700, 600, 550 is illustrated. In one embodiment, the molecular weight of the poly (meth) acrylate having five or more (meth) acryloyl groups is compatible with the polymer (A), antistatic property of the cured film, transparency, hardness, and scratch resistance. From the viewpoint of properties and the like, about 550 to 10000 is preferable, and about 550 to 7000 is more preferable.
なお、本開示において、単に「分子量」と記載する場合、下記の意味を有する。すなわち、ジペンタエリスリトールポリ（メタ）アクリレートのように特定の化学式で一義的に化合物の構造を表現できる（すなわち分子量分布が１である）場合、上記分子量は式量を意味する。一方、ポリマーポリ（メタ）アクリレートのように特定の化学式で一義的に化合物の構造を表現できない（すなわち分子量分布が１より大きい）場合、上記分子量は重量平均分子量を意味する。 In addition, in this indication, when it only describes as "molecular weight", it has the following meaning. That is, in the case where the compound structure can be uniquely represented by a specific chemical formula (ie, the molecular weight distribution is 1) as in dipentaerythritol poly (meth) acrylate, the above molecular weight means the formula weight. On the other hand, when the structure of the compound can not be uniquely represented by a specific chemical formula (i.e., the molecular weight distribution is larger than 1) as in the case of polymer poly (meth) acrylate, the above molecular weight means weight average molecular weight.
また、５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートの水酸基価の上限及び下限は、１００、９０、７５、５０、２５、１０、５、０ｍｇＫＯＨ／ｇ等が例示される。１つの実施形態において、５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートの水酸基価は、ポリマー（Ａ）との相溶性、硬化皮膜の帯電防止性、透明性、硬度、及び耐擦傷性等の観点から、０〜１００ｍｇＫＯＨ／ｇ程度が好ましく、５〜９０ｍｇＫＯＨ／ｇ程度がより好ましい。 The upper limit and the lower limit of the hydroxyl value of the poly (meth) acrylate having five or more (meth) acryloyl groups are, for example, 100, 90, 75, 50, 25, 10, 5, 0 mg KOH / g and the like. In one embodiment, the hydroxyl value of the poly (meth) acrylate having five or more (meth) acryloyl groups is compatible with the polymer (A), antistatic property of the cured film, transparency, hardness, and resistance From the viewpoint of scratch resistance etc., about 0 to 100 mg KOH / g is preferable, and about 5 to 90 mg KOH / g is more preferable.
組成物固形分の全質量に対する５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートの含有量の上限及び下限は、８０、７０、６０、５０、４０、３０、２０、１０、５、０質量％等が例示される。１つの実施形態において、組成物固形分の全質量に対して、５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートを０〜８０質量％含むことが好ましい。 The upper limit and the lower limit of the content of poly (meth) acrylate having five or more (meth) acryloyl groups with respect to the total mass of the composition solid content are 80, 70, 60, 50, 40, 30, 20, 10, 5 , 0 mass%, etc. are illustrated. In one embodiment, it is preferable to include 0 to 80% by mass of poly (meth) acrylate having 5 or more (meth) acryloyl groups based on the total mass of the composition solid content.
（反応性希釈剤）
反応性希釈剤は、上記「５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレート」以外の炭素−炭素不飽和結合等の活性エネルギー線反応性官能基を有する化合物である。反応性希釈剤は２種以上を併用してもよい。反応性希釈剤を併用することによって、ポリマー（Ａ）と５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレートの相溶性が一層良好になる。その結果、本発明に係る活性エネルギー線硬化性樹脂組成物の透明性が向上し、かつ、帯電防止性、透明性、硬度、及び耐擦傷性等に特に優れた硬化皮膜が得られる。
(Reactive diluent)
The reactive diluent is a compound having an active energy ray-reactive functional group such as a carbon-carbon unsaturated bond other than the above-mentioned "poly (meth) acrylate having 5 or more (meth) acryloyl groups". Two or more reactive diluents may be used in combination. By using a reactive diluent in combination, the compatibility between the polymer (A) and the poly (meth) acrylate having 5 or more (meth) acryloyl groups is further improved. As a result, the transparency of the active energy ray curable resin composition according to the present invention is improved, and a cured film which is particularly excellent in antistatic property, transparency, hardness, scratch resistance and the like can be obtained.
反応性希釈剤は、テトラ（メタ）アクリレート、トリ（メタ）アクリレート、ジ（メタ）アクリレート、上記モノマー（ａ１’）〜（ａ３’）、上記炭素数１〜１０程度の炭化水素基を有するモノ（メタ）アクリレート、上記芳香環構造含有ビニルモノマー等が例示される。特に相溶化作用と硬化皮膜性能（硬度、耐擦傷性等）の観点よりトリ（メタ）アクリレート、テトラ（メタ）アクリレートが好ましい。 The reactive diluent is a monomer having tetra (meth) acrylate, tri (meth) acrylate, di (meth) acrylate, the above monomers (a1 ′) to (a3 ′), and the above hydrocarbon group having about 1 to 10 carbon atoms. Examples thereof include (meth) acrylates and the above aromatic ring structure-containing vinyl monomers. In particular, tri (meth) acrylate and tetra (meth) acrylate are preferable from the viewpoint of the compatiblizing action and the cured film performance (hardness, scratch resistance, etc.).
テトラ（メタ）アクリレートは、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）アクリレート等が例示される。 Examples of tetra (meth) acrylates include pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate.
トリ（メタ）アクリレートは、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等が例示される。 Examples of tri (meth) acrylates include pentaerythritol tri (meth) acrylate and trimethylolpropane tri (meth) acrylate.
ジ（メタ）アクリレートは、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ヘキサエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジシクロペンタジエンジ（メタ）アクリレート、ビスフェノールＡエチレンオキシド変性ジ（メタ）アクリレート等が例示される。 Di (meth) acrylates are 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexa Examples thereof include ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate and the like.
（光重合開始剤）
１つの実施形態において、上記活性エネルギー線硬化性樹脂組成物には、光重合開始剤が含まれる。光重合開始剤は２種以上を併用してもよい。光重合開始剤は、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−モルホリノプロパン−１−オン、２，４，６−トリメチルベンゾイル−ジフェニル−ホスフィンオキサイド、４−メチルベンゾフェノン等が例示される。なお、光重合開始剤は、紫外線硬化を行なう場合に使用されるが、電子線硬化をする場合には、必ずしも必要ではない。
(Photopolymerization initiator)
In one embodiment, the active energy ray-curable resin composition contains a photopolymerization initiator. You may use together 2 or more types of photoinitiators. Photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-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, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 4-methyl benzophenone etc. is illustrated. In addition, although a photoinitiator is used when performing an ultraviolet curing, when performing an electron beam curing, it is not necessarily required.
光重合開始剤の含有量は、特に制限されない。組成物１００質量部に対する光重合開始剤の含有量の上限及び下限は、１５、１４、１０、９、８、７、６、５、４、３、２、１、０．５、０質量部等が例示される。組成物中に光重合開始剤が含まれる場合、１つの実施形態において、組成物固形分１００質量部に対し、光重合開始剤を（メタ）アクリロイル基の反応進行の観点から、０．５〜１５質量部が好ましく、０．５〜１０質量部程度含むことがより好ましい。 The content of the photopolymerization initiator is not particularly limited. The upper limit and the lower limit of the content of the photopolymerization initiator relative to 100 parts by mass of the composition are 15, 14, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0 parts by mass Etc. are illustrated. When the composition contains a photopolymerization initiator, in one embodiment, the photopolymerization initiator is 0.5 to 0.5 parts of the solid content of the composition from the progress of the reaction of the (meth) acryloyl group, relative to 100 parts by mass of the composition. 15 parts by mass is preferable, and about 0.5 to 10 parts by mass is more preferable.
ポリマー（Ａ）１００質量部に対する光重合開始剤の含有量の上限及び下限は、５０、４５、４０、３５、３０、２５、２０、１５、１０、９、８、７、６、５、４、３、２、１、０．５、０質量部等が例示される。組成物中に光重合開始剤が含まれる場合、１つの実施形態において、ポリマー（Ａ）１００質量部に対し、光重合開始剤の含有量は、（メタ）アクリロイル基の反応進行の観点から、０．５〜５０質量部が好ましく、５〜２０質量部程度がより好ましい。 The upper limit and the lower limit of the content of the photopolymerization initiator relative to 100 parts by mass of the polymer (A) are 50, 45, 40, 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4 , 3, 2, 1, 0.5, 0 parts by mass, etc. are exemplified. When the composition contains a photopolymerization initiator, in one embodiment, the content of the photopolymerization initiator is 100% by mass of the polymer (A) from the viewpoint of the reaction progress of the (meth) acryloyl group, 0.5-50 mass parts is preferable, and about 5-20 mass parts is more preferable.
（添加剤）
上記組成物は、上記ポリマー（Ａ）、希釈溶剤、５個以上の（メタ）アクリロイル基を有するポリ（メタ）アクリレート、反応性希釈剤、光重合開始剤のいずれでもない剤を添加剤として含み得る。添加剤は２種以上を併用してもよい。添加剤は、上述したもの等が例示される。
(Additive)
The composition contains, as an additive, an agent which is not any of the polymer (A), a diluent, a poly (meth) acrylate having 5 or more (meth) acryloyl groups, a reactive diluent, and a photopolymerization initiator. obtain. The additives may be used in combination of two or more. Examples of the additive include those described above.
１つの実施形態において、添加剤含有量は、組成物固形分１００質量部に対して、０〜６０質量部、４０質量部未満、２５質量部未満、１０質量部未満、５質量部未満、１質量部未満、０．１質量部未満、０．０１質量部未満、０質量部等が例示される。 In one embodiment, the additive content is 0 to 60 parts by mass, less than 40 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass, relative to 100 parts by mass of the composition solid content Less than 0.1 parts by weight, less than 0.01 parts by weight, 0 parts by weight and the like are exemplified.
[硬化物]
本開示は、上記活性エネルギー線硬化性樹脂組成物の硬化物を提供する。上記硬化物は、上記活性エネルギー線硬化性樹脂組成物に、紫外線、電子線、放射線等の活性エネルギー線を照射することにより得られる。
[Cured product]
The present disclosure provides a cured product of the above-described active energy ray-curable resin composition. The said cured | curing material is obtained by irradiating active energy rays, such as an ultraviolet-ray, an electron beam, a radiation, etc., to the said active energy ray curable resin composition.
硬化反応に用いる活性エネルギー線は、紫外線や電子線が例示される。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、８０〜１６０Ｗ／ｃｍ程度のランプ出力を有するランプ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、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ことが好ましい。 The active energy ray used for the curing reaction is exemplified by ultraviolet ray and electron beam. As a light source of ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, and a metal halide lamp can be used. The amount of light, the arrangement of light sources, the transfer speed, etc. can be adjusted as necessary. For example, when using a high pressure mercury lamp, the transfer speed is 5 to 50 m for one lamp having a lamp output of about 80 to 160 W / cm. It is preferable to cure at about / minute. On the other hand, in the case of an electron beam, it is preferable to cure at a transport speed of about 5 to 50 m / min with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV.
[フィルム]
本開示は、上記硬化物を含む、フィルムを提供する。上記フィルムは、上記硬化物と各種ベースフィルムとを構成要素とする物品である。１つの実施形態において、上記フィルムはプラスチックフィルムである。
[the film]
The present disclosure provides a film comprising the above-mentioned cured product. The film is an article having the cured product and various base films as components. In one embodiment, the film is a plastic film.
ベースフィルム（基材）は各種公知のものを採用できる。ベースフィルムは、ポリカーボネートフィルム、アクリルフィルム（ポリメチルメタクリレートフィルム等）、ポリスチレンフィルム、ポリエステルフィルム、ポリオレフィンフィルム、エポキシ樹脂フィルム、メラミン樹脂フィルム、トリアセチルセルロースフィルム、ＡＢＳフィルム、ＡＳフィルム、ノルボルネン系樹脂フィルム、環状オレフィンフィルム、ポリビニルアルコールフィルム等が例示される。ベースフィルムの厚みは特に限定されないが、１５〜１００μｍ程度が好ましい。 Various known films can be adopted as the base film (substrate). The base film is a polycarbonate film, an acrylic film (polymethyl methacrylate film etc.), a polystyrene film, a polyester film, a polyolefin film, an epoxy resin film, a melamine resin film, a triacetyl cellulose film, an ABS film, an AS film, a norbornene resin film, A cyclic olefin film, a polyvinyl alcohol film, etc. are illustrated. The thickness of the base film is not particularly limited, but is preferably about 15 to 100 μm.
上記フィルムは各種公知の方法で製造できる。フィルムの製造方法は、上記活性エネルギー線硬化性樹脂組成物を上記ベースフィルムの少なくとも片面に塗工し、必要に応じて乾燥させてから、活性エネルギー線を照射する方法等が例示される。また、得られたベースフィルムの非塗工面に本実施形態に係る樹脂組成物を塗工し、その上に他のベースフィルムを貼り合わせてから活性エネルギー線を照射することで積層フィルムを製造することもできる。 The film can be produced by various known methods. As a method for producing a film, a method of applying the active energy ray curable resin composition on at least one side of the base film, drying it as necessary, and irradiating the active energy ray is exemplified. In addition, the resin composition according to the present embodiment is coated on the non-coated surface of the obtained base film, and another base film is bonded thereon, and then a laminated film is manufactured by irradiating active energy rays. It can also be done.
塗工方法は、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、スクリーン印刷等が例示される。 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, flexo printing, screen printing and the like.
塗工量は特に限定されないが、乾燥後の質量が０．１〜３０ｇ／ｍ２程度が好ましく、１〜２０ｇ／ｍ２がより好ましい。 Although not coated amount is particularly limited, the mass after drying is preferably about 0.1 to 30 g / m 2, more preferably from 1 to 20 g / m 2.
以下に実施例及び比較例をあげて本発明をより具体的に説明する。本発明は、以下の実施例に限定されない。なお、以下において「部」及び「％」は、特に説明がない限り、それぞれ質量部及び質量％を示す。 Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. The present invention is not limited to the following examples. In addition, "part" and "%" respectively show a mass part and mass%, unless there is particular explanation below.
また、（Ａ）成分の重量平均分子量は、市販の分子量測定機を利用し、以下の条件で測定した実測値である。
分子量測定機：製品名「ＨＬＣ−８３２０ＧＰＣ」、東ソー（株）製
カラム：製品名「ＴＳＫｇｅｌ Ｇ６０００ＰＷＸＬ−ＣＰ」、「ＴＳＫｇｅｌ Ｇ３０００ＰＷＸＬ−ＣＰ」、東ソー（株）製
展開溶剤：０．１ＭのＮａＮＯ３及び０．１Ｍの酢酸溶液
流速：０．５ｍＬ／ｍｉｎ
試料濃度：０．５ｇ／Ｌ
標準物質：ポリエチレンオキサイド（ＴＳＫｇｅｌ標準ポリエチレンオキサイド ＳＥ-キット 東ソー（株）製）
Moreover, the weight average molecular weight of (A) component is the actual value measured on condition of the following using the commercially available molecular weight measuring machine.
Molecular weight measurement machine: Product name "HLC-8320GPC", Tosoh Corp. column: Product name "TSKgel G6000PW XL- CP", "TSKgel G3000PW XL- CP", Tosoh Corp. development solvent: 0.1 M NaNO Acetic acid solution flow rate of 3 and 0.1 M: 0.5 mL / min
Sample concentration: 0.5 g / L
Reference material: polyethylene oxide (TSKgel standard polyethylene oxide SE-kit Tosoh Co., Ltd.)
＜（ａ２）成分の合成＞
合成例１
撹拌装置、冷却管を備えた反応装置に、ヒドロキシエチルメタクリレート１３０部、ε−カプロラクトン１１４０部及びオクチル酸スズ１．３部を加え、１５０℃まで昇温し、６時間保温した後に冷却して、重量平均分子量が約２７５０である水酸基含有ビニルモノマーとラクトンとの開環重付加物（以下、（ａ２−１）成分という。）を得た。
<Synthesis of (a2) Component>
Synthesis example 1
130 parts of hydroxyethyl methacrylate, 1140 parts of ε-caprolactone and 1.3 parts of tin octylate are added to a reaction apparatus equipped with a stirrer and a condenser, heated to 150 ° C., kept warm for 6 hours and then cooled, A ring-opening polyadduct of a hydroxyl group-containing vinyl monomer having a weight average molecular weight of about 2750 and a lactone (hereinafter, referred to as component (a2-1)) was obtained.
なお、当該重量平均分子量は、市販の分子量測定機（本体製品名「ＨＬＣ−８２２０ＧＰＣ」、東ソー（株）製；カラム製品名「ＴＳＫｇｅｌ ＳｕｐｅｒＨＺ−Ｍ」、東ソー（株）製）を用いて、展開溶剤：テトラヒドロフラン流速：０．３５ｍＬ／ｍｉｎ試料濃度：０．５％
標準物質：ポリスチレン（標準ポリスチレンキット ＰＳｔＱｕｉｃｋＡ、Ｂ、Ｃ 東ソー（株）製）
という条件で測定したことにより得た値である（以下、同様）。表１に組成と重量平均分子量を示す（以下、同様）。
In addition, the said weight average molecular weight develops using a commercially available molecular weight measuring machine (the main product name "HLC-8220GPC", Tosoh Corp. product; column product name "TSKgel SuperHZ-M", Tosoh Corp. product) Solvent: Tetrahydrofuran Flow rate: 0.35 mL / min Sample concentration: 0.5%
Reference material: Polystyrene (Standard polystyrene kit PStQuick A, B, C Tosoh Co., Ltd.)
It is a value obtained by measuring under the condition (following, the same). The composition and weight average molecular weight are shown in Table 1 (the same applies hereinafter).
＜（Ａ）成分の合成＞
製造例１
合成例１と同様の反応装置に、メタクリロイルオキシエチルトリメチルアンモニウムクロリド（ＤＭＣ）（以下、（ａ１−１）成分という。）１００部、（ａ２−１）成分８０部、ｔｅｒｔ−ブチルメタアクリレート（ｔＢＭＡ）（以下、（ａ３−１）成分という。）２０部及びプロピレングリコールモノメチルエーテル（以下、ＰＧＭという。）８００部を加え、８０℃まで昇温した。次いで２，２’−アゾビス（メチルブチロニトリル）（以下、ＡＭＢＮという。）８部及びＰＧＭ３２部を加え、重合反応を開始、８５℃で６時間保温した後に冷却し、四級アンモニウム塩構造含有ポリマー（Ａ−１）の溶液（不揮発分２０％）を得た。
<Synthesis of (A) Component>
Production Example 1
In a reaction apparatus similar to Synthesis Example 1, 100 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC) (hereinafter referred to as component (a1-1)), 80 parts of component (a2-1), tert-butyl methacrylate (tBMA) 20 parts of (hereinafter referred to as component (a3-1)) and 800 parts of propylene glycol monomethyl ether (hereinafter referred to as PGM) were added, and the temperature was raised to 80 ° C. Then, 8 parts of 2,2'-azobis (methylbutyronitrile) (hereinafter referred to as AMBN) and 32 parts of PGM are added, polymerization reaction is initiated, and the mixture is kept at 85 ° C for 6 hours and cooled to contain quaternary ammonium salt structure. The solution (20% of non volatile matter) of a polymer (A-1) was obtained.
製造例２〜６及び比較製造例１〜４
表１に記載するように成分を変更した以外は製造例１と同様にして実施した。
ｉＢＭＡ：イソブチルメタアクリレート
ＣＨＭＡ：シクロヘキシルメタクリレート
ＬＭＡ：ラウリルメタクリレート
Production Examples 2 to 6 and Comparative Production Examples 1 to 4
The procedure was carried out in the same manner as in Production Example 1 except that the components were changed as described in Table 1.
＜活性エネルギー線硬化性樹脂組成物の調製＞
実施例１
溶液状の（Ａ−１）成分からなる帯電防止剤を５部、ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）（ＭＩＷＯＮ製、商品名「ＭＩＲＡＭＥＲ Ｍ６００」）を５０部、ウレタンアクリレート（荒川化学工業（株）製、商品名「ビームセット５７７」）を５０部、及び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」）を２部、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−２−プロパン−２−オン（ＢＡＳＦジャパン（株）製、商品名「イルガキュアー２９５９」）を３部、固形分割合で配合し、ＰＧＭで希釈して、不揮発分３０％の活性エネルギー線硬化性樹脂組成物を調製した。
<Preparation of Active Energy Ray-Curable Resin Composition>
Example 1
5 parts of an antistatic agent consisting of solution (A-1) component, 50 parts of dipentaerythritol hexaacrylate (DPHA) (manufactured by MIWON, trade name “MIRAMER M600”), urethane acrylate (Arakawa Chemical Industries, Ltd.) Product, 50 parts of trade name "Beam set 577", and 2 parts of 1-hydroxy-cyclohexyl-phenyl ketone (BASF Japan Ltd., trade name "IRGACURE 184"), 1- [4- (2) 3 parts of 3-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-2-propan-2-one (manufactured by BASF Japan Ltd., trade name “IRGACURE 2959”) are blended in a solid content ratio, It diluted with PGM and prepared the active energy ray curable resin composition of 30% of a non volatile matter.
実施例２〜６及び比較例１〜４
表２に記載するように成分を変更した以外は実施例１と同様にして実施した。
It carried out like Example 1 except having changed the component as described in Table 2, and implemented.
（フィルムの作製）
１００μｍ膜厚のＰＥＴフィルム（東レ（株）製 ルミラー１００Ｕ４８３）上に、各活性エネルギー線硬化性樹脂組成物を、硬化後の被膜の膜厚が５μｍとなるように＃１５バーコーターにて塗布し、８０℃で１分間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、硬化被膜を供えたフィルムを得た。作製したフィルムに対する下記の評価結果を表２に示す。
(Production of film)
Each active energy ray curable resin composition was coated on a 100 μm thick PET film (Lumirror 100U483 manufactured by Toray Industries, Inc.) so that the film thickness of the cured film would be 5 μm with a # 15 bar coater. The film was made to dry at 80 ° C. for 1 minute. Subsequently, the film obtained was provided with a cured film using a UV curing device (product name: UBT-080-7A / BM, manufactured by Multiply, high pressure mercury lamp 600 mJ / cm 2 ). The following evaluation results for the produced film are shown in Table 2.
＜帯電防止性試験＞
フィルムの作製直後の表面抵抗を、市販抵抗率計（三菱化学（株）製、製品名「ハイレスタＭＣＰ−ＨＴ−４５０」）を用い、ＪＩＳ Ｋ ６９１１に準じ、印加電圧５００Ｖで測定した。
１×１０１１Ω／ｓｑ≧・・・〇
１×１０１１Ω／ｓｑ＜・・・×
<Antistatic test>
The surface resistance immediately after the preparation of the film was measured at an applied voltage of 500 V according to JIS K 6911 using a commercially available resistivity meter (manufactured by Mitsubishi Chemical Co., Ltd., product name "Hiresta MCP-HT-450").
1 × 10 11 Ω / sq ・ ・ ・... 1 × 10 11 Ω / sq <.
＜透明性測定＞
フィルムのヘイズ値を、村上色彩技術研究所製カラーへイズメーターを用いて測定した。
１．０≧・・・〇
１．０＜・・・×
<Transparency measurement>
The haze value of the film was measured using a color haze meter made by Murakami Color Research Laboratory.
1.0 ・ ・ ・ ... 1.0 1.0 <...
＜耐湿熱性試験＞
フィルムを温度８０℃、湿度９５％Ｒｈ環境下に２４時間静置した後、フィルム表面への表面析出物の有無を目視で確認した。
表面析出物なし・・・〇
表面析出物有り・・・×
<Modified heat resistance test>
After the film was allowed to stand for 24 hours in an environment of temperature 80 ° C. and humidity 95% Rh, the presence or absence of surface precipitate on the film surface was visually confirmed.
No surface deposit ... 〇 Surface deposit present ... ×
＜耐擦傷性試験＞
フィルムの硬化皮膜を、スチールウール（１０ｍｍ×１０ｍｍ）を底に貼り付けた重り（５００ｇ）で１０回擦り、塗膜外観を基準で目視評価した。
傷なし・・・〇
傷有り・・・×
<Abrasion resistance test>
The cured film of the film was rubbed ten times with a weight (500 g) attached to the bottom of steel wool (10 mm × 10 mm) and visually evaluated based on the appearance of the coating.
No damage · · · · · · · · ×
Claims (4)
水酸基含有ビニルモノマーとラクトンとの開環重付加物であり、かつ、
重量平均分子量が１，０００〜１０，０００であるビニルモノマー由来の構成単位（ａ２）、
及び
炭素数３〜５の分岐アルキルエステル基を含むビニルモノマー由来の構成単位（ａ３）を含み、
分子量分布（Ｍｗ／Ｍｎ）が１．８〜５．０である、ポリマー（Ａ）を含む、
活性エネルギー線硬化性樹脂組成物用帯電防止剤。 Structural unit (a1) derived from a vinyl monomer containing quaternary ammonium salt structure,
A ring-opening polyadduct of a hydroxyl group-containing vinyl monomer and a lactone, and
Component units (a2) derived from a vinyl monomer having a weight average molecular weight of 1,000 to 10,000,
And a structural unit (a3) derived from a vinyl monomer containing a branched alkyl ester group having 3 to 5 carbon atoms,
A polymer (A), having a molecular weight distribution (Mw / Mn) of 1.8 to 5.0,
Antistatic agent for active energy ray curable resin composition.
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| JP2009040924A (en) * | 2007-08-10 | 2009-02-26 | Soken Chem & Eng Co Ltd | Curable resin composition and high transparency antistatic hard coat material using the same |
| JP6400112B2 (en) * | 2014-09-29 | 2018-10-03 | 富士フイルム株式会社 | Active energy ray-curable composition and antistatic film |
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| JP2008308533A (en) * | 2007-06-13 | 2008-12-25 | Toyo Ink Mfg Co Ltd | Antistatic pressure-sensitive adhesive composition and laminated product thereof |
| JP2009173875A (en) * | 2007-12-25 | 2009-08-06 | Nippon Synthetic Chem Ind Co Ltd:The | Crosslinkable resin composition, adhesive for optical member, and optical member |
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