JP2012201880A - Active energy ray-curable ink composition - Google Patents
Active energy ray-curable ink composition Download PDFInfo
- Publication number
- JP2012201880A JP2012201880A JP2011071223A JP2011071223A JP2012201880A JP 2012201880 A JP2012201880 A JP 2012201880A JP 2011071223 A JP2011071223 A JP 2011071223A JP 2011071223 A JP2011071223 A JP 2011071223A JP 2012201880 A JP2012201880 A JP 2012201880A
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- meth
- unsaturated double
- ethylenically unsaturated
- active energy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000000049 pigment Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 57
- 239000000976 ink Substances 0.000 description 25
- -1 for example Polymers 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 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 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 3
- RKLJSBNBBHBEOT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropanoyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)C(=O)OC(=O)C(C)(C)CO RKLJSBNBBHBEOT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
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- 229920002554 vinyl polymer Polymers 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-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
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- KXZLHMICGMACLR-UHFFFAOYSA-N 2-(hydroxymethyl)-2-pentylpropane-1,3-diol Chemical compound CCCCCC(CO)(CO)CO KXZLHMICGMACLR-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
- XNLHQURWXIWCDF-UHFFFAOYSA-N 2-[4-[2,4-dihydroxy-2,4-dimethyl-3-oxo-5-[4-(2-prop-2-enoyloxyethoxy)phenyl]pentyl]phenoxy]ethyl prop-2-enoate Chemical compound C=1C=C(OCCOC(=O)C=C)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCOC(=O)C=C)C=C1 XNLHQURWXIWCDF-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
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- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical compound C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- KOEVABCENPYWCU-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrachlorophenyl)methanone Chemical compound ClC1=C(Cl)C(Cl)=CC(C(=O)C=2C=CC=CC=2)=C1Cl KOEVABCENPYWCU-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、硬化性能と柔軟性能の両立が可能な活性エネルギー線硬化型インキ組成物に関する。 The present invention relates to an active energy ray-curable ink composition capable of achieving both curing performance and flexibility performance.
活性エネルギー線硬化型インキを構成する成分は、樹脂、モノマー、顔料、開始剤、その他補助剤に大別することができ、モノマー成分においては一分子中に存在するエチレン性不飽和二重結合の数が多いものは硬化性能が高く柔軟性能が低い。一方でエチレン性不飽和二重結合の数が少ないものは硬化性能が低く柔軟性能が高いことが知られている。 The components constituting the active energy ray-curable ink can be broadly classified into resins, monomers, pigments, initiators, and other auxiliary agents. In the monomer components, ethylenically unsaturated double bonds existing in one molecule. A large number has high curing performance and low flexibility. On the other hand, those having a small number of ethylenically unsaturated double bonds are known to have low curing performance and high flexibility performance.
硬化性能が低いインキでは、印刷時のインキ硬化が不十分になる場合があり、インキ硬化が不十分だと印刷表面の擦れや積み重ねたとき上の印刷物の裏面にインキが付着するブロッキングのトラブルを引き起こすことがある。 Ink with low curing performance may cause insufficient ink curing at the time of printing. If ink curing is insufficient, the printing surface will be rubbed or the ink will adhere to the back of the printed matter when stacked. May cause.
柔軟性能が低いインキでは、印刷物が製函工程等で折り曲げられたときにインキ皮膜が開裂する罫線割れのトラブルを引き起こすことがある。 Ink with low flexibility performance may cause trouble of ruled line cracking that the ink film is cleaved when the printed matter is bent in a box making process or the like.
一般に活性エネルギー線硬化型インキにおいて、硬化性能を得るためにはエチレン性不飽和二重結合の数が多いモノマーを用い、柔軟性能を得るためにはエチレン性不飽和二重結合の数が少ないモノマーを用いる。硬化性能と柔軟性能は相反する性能であるため、その両立は難しい。 In general, in an active energy ray-curable ink, a monomer having a large number of ethylenically unsaturated double bonds is used to obtain curing performance, and a monomer having a small number of ethylenically unsaturated double bonds is used to obtain flexibility. Is used. Since curing performance and flexibility performance are contradictory, it is difficult to achieve both.
本発明は、硬化性能と柔軟性能に優れた活性エネルギー線硬化型インキ組成物を提供することを目的とする。 An object of the present invention is to provide an active energy ray-curable ink composition excellent in curing performance and flexibility performance.
本発明者等は、鋭意検討を行った結果、バインダー樹脂、特定のエチレン性不飽和二重結合を有するモノマー、光重合開始剤および顔料を含有する活性エネルギー線硬化型インキは、硬化性能と柔軟性能に優れたことを見出し、本発明を完成するに至った。
すなわち、本発明は、インキ全量に対して、１〜２０重量％のバインダー樹脂、１０〜８０重量％のエチレン性不飽和二重結合を有するモノマー、光重合開始剤および顔料を含有する活性エネルギー線硬化型インキにおいて、
エチレン性不飽和二重結合を有するモノマーが、
エチレン性不飽和二重結合を４官能有するモノマーを１種類以上
かつ、
エチレン性不飽和二重結合を５官能以上有するモノマーを２種類以上であることを特徴とする活性エネルギー線硬化型インキに関するものである。
As a result of intensive studies, the present inventors have found that an active energy ray-curable ink containing a binder resin, a monomer having a specific ethylenically unsaturated double bond, a photopolymerization initiator, and a pigment has excellent curing performance and flexibility. It was found that the performance was excellent, and the present invention was completed.
That is, the present invention relates to an active energy ray containing 1 to 20% by weight of a binder resin, 10 to 80% by weight of a monomer having an ethylenically unsaturated double bond, a photopolymerization initiator and a pigment based on the total amount of the ink. In curable ink,
A monomer having an ethylenically unsaturated double bond is
One or more monomers having four functional ethylenically unsaturated double bonds
And,
The present invention relates to an active energy ray-curable ink characterized by having two or more types of monomers having five or more functional ethylenically unsaturated double bonds.
さらに、本発明は、前記エチレン性不飽和二重結合を４官能有するモノマーまたはエチレン性不飽和二重結合を５官能以上有するモノマーのうち少なくとも３種類のモノマーが、インキ全量に対して、２重量％以上であることを特徴とする上記の活性エネルギー線硬化型インキに関するに関するものである。
また、本発明は、エチレン性不飽和二重結合を４官能有するモノマーおよびエチレン性不飽和二重結合を５官能以上有するモノマーが、
重量平均分子量６００以上のモノマー２種類
および
重量平均分子量６００未満のモノマー１種類を含んでいることを特徴とする上記の活性エネルギー線硬化型インキに関するものである。
Further, according to the present invention, at least three kinds of monomers having 4 functional ethylenically unsaturated double bonds or 5 or more ethylenically unsaturated double bonds have a weight of 2 wt. % Or more of the active energy ray-curable ink.
In the present invention, a monomer having four functional ethylenically unsaturated double bonds and a monomer having five or more ethylenically unsaturated double bonds are
The present invention relates to the above active energy ray-curable ink, comprising two types of monomers having a weight average molecular weight of 600 or more and one type of monomers having a weight average molecular weight of less than 600.
本発明により、硬化性能と柔軟性能の両方に優れた活性エネルギー線硬化型インキ組成物を提供することが可能となった。 According to the present invention, it is possible to provide an active energy ray-curable ink composition excellent in both curing performance and flexibility performance.
単純にエチレン性不飽和二重結合の多いモノマーと少ないモノマーを併用するだけでは硬化性能と柔軟性能の両立は発現せず、エチレン性不飽和二重結合を４官能有するモノマーとエチレン性不飽和二重結合を５官能以上有するモノマーを３種類以上用い、これらのうち少なくとも1種類は重量平均分子量６００以下のモノマーを用いることで硬化性能を発現し、且つ、これらのうち少なくとも２種類は重量平均分子量６００以上のモノマーを用いることで柔軟性能を発現し、硬化性能と柔軟性能の両立を可能にしたと考える。 Simply combining a monomer having a large amount of ethylenically unsaturated double bonds and a monomer having a small amount does not achieve both curing performance and flexibility, and a monomer having tetrafunctional ethylenically unsaturated double bonds and an ethylenically unsaturated dimer. Three or more types of monomers having 5 or more heavy bonds are used, and at least one of them exhibits curing performance by using a monomer having a weight average molecular weight of 600 or less, and at least two of these have a weight average molecular weight. It is considered that the use of 600 or more monomers allowed for the development of softness performance, making it possible to achieve both curing performance and softness performance.
本発明で使用する、活性エネルギー線とは、紫外線、電子線のことであるが、必ずしもこれに限定されるものではない。 The active energy rays used in the present invention are ultraviolet rays and electron beams, but are not necessarily limited thereto.
本発明で使用するエチレン性不飽和二重結合を有するモノマーとは、アクリレートモノマー、メタクリレートモノマー、ビニルモノマーのことであるが、必ずしもこれに限定されるものではない。 The monomer having an ethylenically unsaturated double bond used in the present invention is an acrylate monomer, a methacrylate monomer, or a vinyl monomer, but is not necessarily limited thereto.
本発明で使用される活性エネルギー線硬化型組成物の組成の例としては、
（ａ）バインダー樹脂 １〜２０重量％
（ｂ）アクリレートモノマー １０〜８０重量％
（ｄ）顔料（有機顔料・無機顔料） ５〜５５重量％
（ｅ）光開始剤、光開始助剤 １〜２０重量％
（ｆ）添加剤 １〜１０重量％
が挙げられる。
As an example of the composition of the active energy ray-curable composition used in the present invention,
(A) 1-20% by weight of binder resin
(B) Acrylate monomer 10-80% by weight
(D) Pigment (organic pigment / inorganic pigment) 5 to 55% by weight
(E) Photoinitiator, photoinitiator auxiliary 1 to 20% by weight
(F) Additive 1 to 10% by weight
Is mentioned.
本発明において使用するバインダー樹脂としては、熱硬化性または熱可塑性樹脂であり、例えば、ポリ塩化ビニル、ポリ（メタ）アクリル酸エステル、エポキシ樹脂、ポリウレタン樹脂、セルロース誘導体（例えば、エチルセルロース、酢酸セルロース、ニトロセルロース）、塩化ビニル酢酸ビニル共重合体、ポリアマイド樹脂、ポリビニルアセタール樹脂、ジアリルフタレート樹脂、ブタジエンーアクリルニトリル共重合体のような合成ゴム等が挙げられる。これらの樹脂は、その中の１種または２種以上を用いることができる。何れもエチレン性不飽和ニ重結合を有するモノマー可溶である樹脂が用いられる。 The binder resin used in the present invention is a thermosetting or thermoplastic resin, for example, polyvinyl chloride, poly (meth) acrylic acid ester, epoxy resin, polyurethane resin, cellulose derivative (for example, ethyl cellulose, cellulose acetate, Nitrocellulose), vinyl chloride vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, and synthetic rubber such as butadiene-acrylonitrile copolymer. These resins can be used alone or in combination of two or more thereof. In either case, a resin that is soluble in a monomer having an ethylenically unsaturated double bond is used.
本発明において、アクリレートモノマーとは単官能または多官能の（メタ）アクリレート類をいい、１０〜８０重量％の範囲で用いられる。 In the present invention, the acrylate monomer refers to monofunctional or polyfunctional (meth) acrylates, and is used in the range of 10 to 80% by weight.
単官能モノマーとしてアルキル（カーボン数が２〜１８）（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレートがあり、さらにベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、トリシクロデカンモノメチロール（メタ）アクリレート等が例示される。 Monofunctional monomers include alkyl (having 2 to 18 carbon atoms) (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl ( Examples thereof include benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecane monomethylol (meth) acrylate.
多官能（メタ）アクリレート類としてはエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（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、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ペンチルグリコールジ（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、ヒドロキシピバリルヒドロキシピバレートジ（メタ）アクリレート（通称マンダ）、ヒドロキシピバリルヒドロキシピバレートジカプロラクトネートジ（メタ）アクリレート、１，６ヘキサンジオールジ（メタ）アクリレート、１，８−オクタンジオールジ（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、１，２−ヘキサデカンジオールジ（メタ）アクリレート、２−メチル−２，４−ペンタンジオールジ（メタ）アクリレート、ビスフェノールＡテトラエチレンオキサイド付加体ジ（メタ）アクリレート、ビスフェノールＦテトラエチレンオキサイド付加体ジ（メタ）アクリレート、水添加ビスフェノールＡテトラエチレンオキサイド付加体ジ（メタ）アクリレート、水添加ビスフェノールＦテトラエチレンオキサイド付加体ジ（メタ）アクリレート、水添加ビスフェノーＡジ（メタ）アクリレート、水添加ビスフェノールＦジ（メタ）アクリレート、グリセリントリ（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、トリメチロールプロパントリカプロラクトネートトリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールヘキサントリ（メタ）アクリレート、トリメチロールオクタントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールテトラエチレンオキサイド付加体（メタ）アクリレート、ジグリセリンテトラ（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、ジトリメチロールプロパンテトラカプロラクトネートテトラ（メタ）アクリレート、ジトリメチロールエタンテトラ（メタ）アクリレート、ジトリメチロールブタンテトラ（メタ）アクリレート、ジトリメチロールヘキサンテトラ（メタ）アクリレート、ジトリメチロールオクタンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールカプロラクトネートヘキサ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールヘプタ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート等を用いることができる。 Polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalyl hydroxypivalate di (meth) acrylate (commonly called manda), Hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,8-octanedio Rudi (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, bisphenol A tetraethylene Oxide adduct di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol F tetraethylene oxide adduct di (meth) Acrylate, water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol group Lopantricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, pentaerythritol tetraethylene oxide adduct (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate tetra (meth) acrylate, ditrimethylolethane Tetra (meth) acrylate, ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meta Acrylate, ditrimethylol octane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol caprolactonate hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate Tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, and the like can be used.
顔料としては、無機顔料および有機顔料を示すことができる。無機顔料としては黄鉛、亜鉛黄、紺青、硫酸バリウム、カドミウムレッド、酸化チタン、亜鉛華、弁柄、アルミナホワイト、炭酸カルシウム、群青、カーボンブラック、グラファイト、アルミニウム粉、ベンガラなどが、有機顔料としては、β−ナフトール系、β−オキシナフトエ酸系、β−オキシナフトエ酸系アニリド系、アセト酢酸アニリド系、ピラゾロン系などの溶性アゾ顔料、β−ナフトール系、β−オキシナフトエ酸系アニリド系、アセト酢酸アニリド系モノアゾ、アセト酢酸アニリド系ジスアゾ、ピラゾロン系などの不溶性アゾ顔料、銅フタロシアニンブルー、ハロゲン化（塩素または臭素化）銅フタロシアニンブルー、スルホン化銅フタロシアニンブルー、金属フリーフタロシアニンなどのフタロシアニン系顔料、キナクリドン系、ジオキサジン系、スレン系（ピラントロン、アントアントロン、インダントロン、アントラピリミジン、フラバントロン、チオインジゴ系、アントラキノン系、ペリノン系、ペリレン系など）、イソインドリノン系、金属錯体系、キノフタロン系などの多環式顔料および複素環式顔料などの公知公用の各種顔料が使用可能である。
本発明に係る顔料は、組成物１００重量％に対して５〜５５重量％の範囲で用いられる。
Examples of the pigment include inorganic pigments and organic pigments. Inorganic pigments such as yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, bengara etc. as organic pigments Are soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetanilide, pyrazolone, β-naphthol, β-oxynaphthoic acid anilide, Insoluble azo pigments such as acetoacetanilide monoazo, acetoacetanilide disazo, pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine , Quinacridone , Dioxazine, selenium (pyrantron, anthanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalone, etc. Various publicly known pigments such as formula pigments and heterocyclic pigments can be used.
The pigment according to the present invention is used in the range of 5 to 55% by weight with respect to 100% by weight of the composition.
本発明で使用される光開始剤としては、水素引き抜き型として、ベンゾフェノン、ｐ−メチルベンゾフェノン、ｐ―クロルベンゾフェノン、テトラクロロベンゾフェノン、ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、ヒドロキシベンゾフェノン、４−ベンゾイル−４’−メチルージフェニルサルファイド、２−イソプロピルチオシサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、アセトフェノン・アリールケトン系開始剤、４，４’−ビス（ジエチルアニノ）ベンゾフェノン、４，４’−ビス（ジメチルアミノ）ベンゾフェノン、ｐ−ジメチルアミノ安息香酸イソアミル、ｐ−ジメチルアミノアセトフェノン・ジアルキルアミノアリールケトン系開始剤、チオキサントン、キサントン系・そのハロゲン置換・多環カルボニル系開始剤などが挙げられる。また、開裂型光開始剤として、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、α―アクリルベンゾイル・ベンゾイン系、ベンジル、２−メチルー２−モルホリノ（４−チオメチルフェニル）プロパンー１−オン、２−ベンジルー２−ジメチルアミノー１−（４−モルホリノフェニル）−１−ブタノン、ベンジルメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシー２−メチルー１−フェニルプロパンー１−オン、１−（４−イソプロピルフェニルー２−ヒドロキシー２−メチルプロパンー１−オン、４−（２−ヒドロキシエトキシ）フェニルー（２−ヒドロキシー２−プロピル）ケトン、４−（２−アクロイルーオキシエトキシ）フェニルー２−ヒドロキシー２−プロピルケトン、ジエトキシアセトフェノンなどがある。 As the photoinitiator used in the present invention, as a hydrogen abstraction type, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, tetrachlorobenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl- 4'-methyl-diphenyl sulfide, 2-isopropylthiocisanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, acetophenone / aryl ketone initiator, 4,4'-bis (Diethylanino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, isoamyl p-dimethylaminobenzoate, p-dimethylaminoacetophenone-dialkylaminoaryl ketone initiator, Xanthone, and the like xanthone Part halogen-substituted and multi-ring carbonyl-based initiators. Further, as a cleavage type photoinitiator, benzoin, benzoin methyl ether, benzoin isopropyl ether, α-acrylbenzoyl benzoin series, benzyl, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, benzylmethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropyl Phenyl-2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4- (2-acryloyloxyethoxy) phenyl-2-hydroxy-2-propyl Ketone And the like diethoxyacetophenone.
また、光開始助剤としては、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン・脂肪族アミン、４，４’−ジエチルアミノベンゾフェノン、２−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル、ジブチルエタノールアミンが挙げられる。
光開始剤は組成物１００重量％に対して組成中に１〜２０重量％の範囲で用いられる。
Photoinitiators include triethanolamine, methyldiethanolamine, triisopropanolamine / aliphatic amine, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Examples thereof include isoamyl dimethylaminobenzoate and dibutylethanolamine.
The photoinitiator is used in the range of 1 to 20% by weight in the composition with respect to 100% by weight of the composition.
一方、組成物中への、添加剤として、耐摩擦、ブロッキング防止、スベリ、スリキズ防止、暗反応防止を目的とする各種添加剤を使用することができ、必要に応じて、レベリング剤、帯電防止剤、界面活性剤、消泡剤、重合禁止剤などを添加してもよい。 On the other hand, various additives for the purpose of anti-friction, anti-blocking, slip, anti-scratch, and dark reaction can be used as additives in the composition. Leveling agents and antistatic agents can be used as necessary. An agent, surfactant, antifoaming agent, polymerization inhibitor and the like may be added.
次に実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの実施例によ
って限定されるものではない。
以下に示す処方により活性エネルギー線硬化型インキ組成物を作成した。
EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by these Examples.
An active energy ray-curable ink composition was prepared according to the following formulation.
（ワニスの作製）
バインダー樹脂とモノマーとを昇温加熱混合（上限温度を１００℃の留め）させ、バインダー樹脂をモノマーに溶解させて樹脂ワニスを作製する。ここでバインダー樹脂としては、ジアリルフタレート樹脂（分子量５００００）を使用したが、必ずしもこれに限定されるものではない。
(Production of varnish)
The binder resin and the monomer are heated and mixed with heating (upper limit temperature is 100 ° C.), and the binder resin is dissolved in the monomer to prepare a resin varnish. Here, diallyl phthalate resin (molecular weight 50000) was used as the binder resin, but it is not necessarily limited thereto.
（インキ組成物の作製）
表１、２の処方により配合した原料を、バタフライミキサーを用いて攪拌混合し、３本ロールにて最大粒径が７．５μｍ以下になるように分散してインキ組成物を作成し、更に樹脂ワニスとモノマーの割合を調整して、インコメーター４００rpm、３０℃の条件でタック値が８．０〜１０．０を示す実施例１〜４、比較例１〜５の活性エネルギー線硬化型インキ組成物を作成した。
(Preparation of ink composition)
The raw materials blended according to the formulations shown in Tables 1 and 2 are stirred and mixed using a butterfly mixer, and dispersed with a three roll so that the maximum particle size is 7.5 μm or less to create an ink composition. The active energy ray-curable ink compositions of Examples 1 to 4 and Comparative Examples 1 to 5 showing a tack value of 8.0 to 10.0 under the conditions of 400 rpm and 30 ° C. by adjusting the ratio of varnish and monomer I made a thing.
＜硬化性能評価＞
各活性エネルギー線硬化型インキ６．０×１０−４（ｍｌ／ｃｍ２）をＲＩテスターにてマリコート紙（北越製紙（株）製コートボール紙）に印刷し、紫外線照射（空冷メタルハライドランプ１２０Ｗ／ｃｍ１灯）後、綿布で擦って皮膜に傷が付かないコンベアスピードで判定した。
（評価基準）
○：コンベアスピード ６０ｍ／分で傷つき無
△：コンベアスピード ６０ｍ／分で傷つき有 ３０ｍ／分で傷つき無
×：コンベアスピード ３０ｍ／分で傷つき有
<Curing performance evaluation>
Each active energy ray-curable ink 6.0 × 10 −4 (ml / cm 2 ) was printed on a maricoat paper (coated cardboard manufactured by Hokuetsu Paper Co., Ltd.) with an RI tester and irradiated with ultraviolet rays (air-cooled metal halide lamp 120W / cm1 light) and then rubbed with a cotton cloth to determine the speed at which the film was not damaged.
(Evaluation criteria)
○: No damage at the conveyor speed of 60 m / min. △: No damage at the conveyor speed of 60 m / min. No damage at 30 m / min. ×: No damage at the conveyor speed of 30 m / min.
＜柔軟性能評価＞
各活性エネルギー線硬化型インキ６．０×１０−４（ｍｌ／ｃｍ２）をＲＩテスターにてマリコート紙（北越製紙（株）製コートボール紙）に印刷し、紫外線照射（空冷メタルハライドランプ１２０Ｗ／ｃｍ１灯）コンベアスピード２０ｍ／分で硬化させ展色物を作成。展色面と反対方向に１８０度折り曲げた後、９０度まで戻したときの展色面のインキ割れの有無を、柔軟性能の指標とした。
（評価基準）
○：割れ無
△：若干の割れ
×：割れ有
<Flexible performance evaluation>
Each active energy ray-curable ink 6.0 × 10 −4 (ml / cm 2 ) was printed on a maricoat paper (coated cardboard manufactured by Hokuetsu Paper Co., Ltd.) with an RI tester and irradiated with ultraviolet rays (air-cooled metal halide lamp 120W / cm1 light) Cured at a conveyor speed of 20 m / min to create a color-exposed product. The presence or absence of ink cracks on the color-developed surface after bending it 180 degrees in the direction opposite to the color-developed surface and returning it to 90 degrees was used as an index of flexibility.
(Evaluation criteria)
○: No cracking △: Some cracking ×: With cracking
表５に示すようにアクリレートモノマーの組み合わせとして、本特許の条件を満たす実施例１〜６の各活性エネルギー線硬化型インキでは、硬化性能、柔軟性能共に良好な結果を示し、硬化性能と柔軟性能が両立できる結果を得た。一方でエチレン性不飽和二重結合を４官能有するモノマーを用いていない比較例１は柔軟性能が劣り、エチレン性不飽和二重結合を５官能以上有するモノマーを用いていない比較例２は硬化性能が劣り、エチレン性不飽和二重結合を４官能以上有し且つ重量平均分子量６００以下のモノマーを用いていない比較例３は硬化性能が劣り、エチレン性不飽和二重結合を４官能以上有し且つ重量平均分子量６００以上のモノマーを用いていない比較例４は柔軟性能が劣り、エチレン性不飽和二重結合を４官能以上有し且つ重量平均分子量６００以上のモノマーを１種類しか用いていない比較例５は柔軟性能が充分でなく、エチレン性不飽和二重結合を４官能または５官能以上有するモノマーを２種類しか用いていない比較例６は、硬化性能が充分でなく且つ柔軟性能も劣る結果となった。
As shown in Table 5, each of the active energy ray curable inks of Examples 1 to 6 satisfying the conditions of this patent as a combination of acrylate monomers showed good results in both curing performance and flexibility performance, and the curing performance and flexibility performance. Obtained a compatible result. On the other hand, Comparative Example 1 that does not use a monomer having four functional ethylenically unsaturated double bonds has poor flexibility, and Comparative Example 2 that does not use a monomer having five or more ethylenically unsaturated double bonds is curing performance. Comparative Example 3 having 4 or more ethylenically unsaturated double bonds and not using a monomer having a weight average molecular weight of 600 or less has poor curing performance and has 4 or more ethylenically unsaturated double bonds. Further, Comparative Example 4 in which a monomer having a weight average molecular weight of 600 or more is not used is inferior in flexibility performance, and a comparison in which only one kind of monomer having four or more functional ethylenically unsaturated double bonds and having a weight average molecular weight of 600 or more is used. Example 5 has insufficient flexibility performance, and Comparative Example 6 using only two types of monomers having four or more ethylenically unsaturated double bonds has sufficient curing performance. Ku and flexible performance also resulted in inferior.
Claims (3)
エチレン性不飽和二重結合を有するモノマーが、
エチレン性不飽和二重結合を４官能有するモノマーを１種類以上
かつ、
エチレン性不飽和二重結合を５官能以上有するモノマーを２種類以上
であることを特徴とする活性エネルギー線硬化型インキ。 In the active energy ray-curable ink containing 1 to 20% by weight of a binder resin, 10 to 80% by weight of a monomer having an ethylenically unsaturated double bond, a photopolymerization initiator and a pigment, based on the total amount of the ink,
A monomer having an ethylenically unsaturated double bond is
One or more monomers having four functional ethylenically unsaturated double bonds, and
An active energy ray-curable ink characterized by comprising two or more monomers having five or more functional ethylenically unsaturated double bonds.
重量平均分子量６００以上のモノマー２種類
および
重量平均分子量６００未満のモノマー１種類
を含んでいることを特徴とする請求項１または２記載の活性エネルギー線硬化型インキ。 A monomer having four functional ethylenically unsaturated double bonds and a monomer having five or more functional ethylenically unsaturated double bonds,
3. The active energy ray-curable ink according to claim 1, comprising 2 types of monomers having a weight average molecular weight of 600 or more and 1 type of monomers having a weight average molecular weight of less than 600. 4.
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| JP2009035730A (en) * | 2007-07-06 | 2009-02-19 | Toyo Ink Mfg Co Ltd | Actinic energy ray curable ink and printed matter |
| JP2009057547A (en) * | 2007-08-03 | 2009-03-19 | Toyo Ink Mfg Co Ltd | Multicolor set of active energy ray-curable ink |
| JP2010000742A (en) * | 2008-06-23 | 2010-01-07 | Dic Corp | Method for manufacturing ultraviolet curable printed material and ultraviolet curable printed material by the method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009035730A (en) * | 2007-07-06 | 2009-02-19 | Toyo Ink Mfg Co Ltd | Actinic energy ray curable ink and printed matter |
| JP2009057547A (en) * | 2007-08-03 | 2009-03-19 | Toyo Ink Mfg Co Ltd | Multicolor set of active energy ray-curable ink |
| JP2010000742A (en) * | 2008-06-23 | 2010-01-07 | Dic Corp | Method for manufacturing ultraviolet curable printed material and ultraviolet curable printed material by the method |
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