JP2007321034A - Uv-curable ink composition for inkjet recording - Google Patents
Uv-curable ink composition for inkjet recording Download PDFInfo
- Publication number
- JP2007321034A JP2007321034A JP2006151597A JP2006151597A JP2007321034A JP 2007321034 A JP2007321034 A JP 2007321034A JP 2006151597 A JP2006151597 A JP 2006151597A JP 2006151597 A JP2006151597 A JP 2006151597A JP 2007321034 A JP2007321034 A JP 2007321034A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- curability
- photopolymerization initiator
- phenyl
- ink composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 67
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 229960003424 phenylacetic acid Drugs 0.000 claims abstract description 9
- 239000003279 phenylacetic acid Substances 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims description 28
- -1 acyl phosphine oxide compound Chemical class 0.000 claims description 16
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 48
- 239000010409 thin film Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 10
- YWEJNVNVJGORIU-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-hydroxy-2-phenylacetate Chemical compound OCCOCCOC(=O)C(O)C1=CC=CC=C1 YWEJNVNVJGORIU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000976 ink Substances 0.000 description 107
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 238000000034 method Methods 0.000 description 18
- 238000007639 printing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical group C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000001035 drying Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920004142 LEXAN™ Polymers 0.000 description 3
- 239000004418 Lexan Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011358 absorbing material Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 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
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-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
- 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 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-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
- 239000001042 pigment based ink Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000243 solution 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、紫外線硬化型インクジェット記録用インク組成物に関するものであり，更に詳しくは，金属，プラスチック等のインク非吸収材料へのフルカラー印刷に適した紫外線硬化型インクジェット記録用プロセスカラーインク組成物に関する。 The present invention relates to an ultraviolet curable ink composition for ink jet recording, and more particularly to a process color ink composition for ultraviolet curable ink jet recording suitable for full color printing on non-ink-absorbing materials such as metals and plastics. .
インクジェットプリンター記録装置による印刷は、ノズルよりインクを噴射し被記録材に付着せしめる方式であり、該ノズルと被記録材が非接触状態にあるため、曲面や凹凸した不規則な形状を有する表面に対して、良好な印刷を行うことができる。このため，産業用途で広範囲にわたる利用分野が期待されている印刷方式である。 Printing by an ink jet printer recording apparatus is a method in which ink is ejected from a nozzle and adhered to a recording material, and since the nozzle and the recording material are in a non-contact state, the surface has a curved surface or an irregular irregular shape. On the other hand, good printing can be performed. For this reason, the printing method is expected to be used in a wide range of industrial applications.
このような印刷方式に用いられるインクジェット記録用インク組成物としては、一般的には、主溶剤として水を用いた水性染料インクと、主溶剤として有機溶剤を用いた油性染料インクとがある。しかしながら、従来の水性染料インクを産業用途で使用する場合の問題点として、非吸収材料上での乾燥速度や、印刷画像の付着性、また耐摩耗性、耐水性、耐光性等の耐久性不良があり、一方、油性染料インクには、クロム等の重金属を含有するクロム錯塩染料を用いていることから、安全性の面で問題があった。そこで、これらの点を改良したインクとして、一つは着色剤に顔料を用いた耐光性の良好な水性顔料及び油性顔料インクが提案されている。また、もう一つとして、近年、産業用途においては、光硬化性材料を含有するインクを紫外線等の活性エネルギー線で硬化、乾燥させることにより、乾燥速度や耐水性の問題を解決し、さらに被膜強度自体を高めた水性及び油性インクが数多く提案されている。そしてこれら２つの利点を併せ持った、顔料を使用した活性エネルギー線硬化型インクジェット記録用インク組成物も提案されている。 Ink jet recording ink compositions used for such printing methods generally include aqueous dye inks using water as the main solvent and oily dye inks using organic solvents as the main solvent. However, problems when using conventional water-based dye inks in industrial applications include drying speed on non-absorbing materials, adhesion of printed images, and poor durability such as wear resistance, water resistance, and light resistance. On the other hand, since the oil-based dye ink uses a chromium complex dye containing a heavy metal such as chromium, there is a problem in terms of safety. Therefore, as an ink improved in these points, one is proposed an aqueous pigment ink and an oil pigment ink having good light resistance using a pigment as a colorant. In addition, in recent years, in industrial applications, ink containing a photocurable material is cured with an active energy ray such as ultraviolet rays and dried to solve the problem of drying speed and water resistance. Many water-based and oil-based inks with increased strength have been proposed. An active energy ray-curable ink composition for ink jet recording using a pigment having both of these two advantages has also been proposed.
このような活性エネルギー線で硬化、乾燥する顔料インクには基本的に水性顔料インクと油性顔料インクがあるが、それらのうち、水性顔料インクについては、インク吸収性の小さい被記録媒体に対して、充分な接着性を付与できないという問題を抱えている。これら被記録媒体に接着性を付与させるべくインク受理層を設ける方法も検討されているが、工程がかさむといった実使用上の問題点を有している。このことから、被記録媒体面に直接印字可能で、硬化被膜の耐久性、接着性に優れた油性顔料インクを用いる方が有利であるとされている。更に印刷物の接着性、耐摩耗性、耐水性等を得るためには、有機溶剤等の非重合性溶剤をほとんど含有しない油性の紫外線硬化型インクを用いる方が有利であり、また活性エネルギー線としては特に紫外線を用いることが設備の設置や取り扱い上簡便でこのましい。このため、非重合性有機溶剤を含有しない油性の紫外線硬化型顔料系インクジェット記録用インク組成物であって、吐出安定性、硬化性、耐久性、保存安定性に優れたインク組成物を開発することが要望されている。 There are basically water-based pigment inks and oil-based pigment inks as pigment inks that are cured and dried with such active energy rays. Have the problem of not being able to give sufficient adhesion. A method of providing an ink receiving layer for imparting adhesiveness to these recording media has also been studied, but has a problem in practical use such that the process becomes bulky. For this reason, it is considered more advantageous to use an oil-based pigment ink that can be directly printed on the surface of a recording medium and has excellent durability and adhesion of a cured coating. Furthermore, in order to obtain adhesiveness, abrasion resistance, water resistance, etc. of printed matter, it is more advantageous to use an oil-based ultraviolet curable ink containing almost no non-polymerizable solvent such as an organic solvent, and as an active energy ray. In particular, the use of ultraviolet rays is convenient and convenient for installation and handling of equipment. Therefore, an oil-based UV-curable pigment-based ink jet recording ink composition that does not contain a non-polymerizable organic solvent and that is excellent in ejection stability, curability, durability, and storage stability is developed. It is requested.
紫外線硬化型インクを用いるインクジェットプリンター記録装置の印刷プロセスとしては、従来の水性インク用インクジェットプリンターと同様、プリントヘッドが被印刷媒体上をスキャンし印刷画像が形成され、プリントヘッドによる各色同時のインク付与に追尾して画像形成部分に逐次紫外線照射が行われる印刷プロセスと、従来の平版印刷、フレキソ印刷装置と同様、プリントヘッドは固定され、被印刷媒体が動いて全面に単色画像を形成してからこれに紫外線照射を行うプロセスを繰り返し、単一色付与と硬化が色順次に行われる印刷プロセスが提案されている。 The printing process of an inkjet printer recording device that uses ultraviolet curable ink is the same as that of conventional inkjet printers for water-based inks. The print head scans the print medium to form a printed image, and the print head applies ink simultaneously for each color. As with conventional lithographic printing and flexographic printing devices, the print head is fixed and the printing medium moves to form a single-color image on the entire surface. A printing process has been proposed in which a process of irradiating ultraviolet rays is repeated, and a single color is imparted and cured in a color sequence.
平版印刷、フレキソ印刷等の従来の印刷プロセスの場合、非吸収材料へのフルカラー印刷物の低濃度部分と高濃度部分とでは印刷画素の大きさに違いはあるものの印刷膜厚に大きな差がないのに対して、前述したインクジェット印刷プロセスの場合、濃度変化を印刷膜厚の差で表現するため低濃度部分と高濃度部分との膜厚の差が大きい。特に、非重合性有機溶剤を含有しないインクの場合、膜厚差はより大きくなる。 In the case of conventional printing processes such as lithographic printing and flexographic printing, there is no significant difference in the printed film thickness, although there is a difference in the size of printing pixels between the low density part and the high density part of the full-color print on the non-absorbing material. On the other hand, in the case of the ink jet printing process described above, the difference in film thickness between the low density portion and the high density portion is large because the change in density is expressed by the difference in print film thickness. In particular, in the case of an ink not containing a non-polymerizable organic solvent, the film thickness difference becomes larger.
このような膜厚差を有する印刷画像の中で、ラジカル重合型の紫外線硬化性インクを用いる場合、印刷画像の薄膜部分において、空気とインクの界面よりインク中に溶解してくる酸素により重合が阻害されることはよく知られている。酸素による重合阻害作用は、印刷被膜表面で発生するが特に薄膜で大きく、重合禁止作用の緩和策としては、特定の開始剤の添加、多官能モノマーの増量、光重合開始剤の増量、光開始助剤の併用等が行われている。
また印刷画像の厚膜部分において、使用されるインク中の光硬化性材料、光重合開始剤によっては、紫外線に対する吸収係数が大きいため塗膜表面でそのほとんどが吸収されてしまい、膜厚方向に均一な硬化が行われず、特に、塗膜表面から遠く基材に近い部分の塗膜強度が不足することがあった。
このように、紫外線硬化型インクの硬化性は、使用する光硬化性材料、光重合開始剤により決定されるが、吐出性の確保のため低粘度の必要なインクジェット記録用インクの場合、反応性が高く、良好な硬化性を有し塗膜強度の高い多官能モノマーの使用は粘度が高いため抑えられ、モノマーの７０％以上は１官能、２官能モノマーを使用して形成されるのが一般的である。このため、硬化性の向上に対しては、光重合開始剤の組成による方が選定の自由度が高くまた硬化性に与える影響も大きい。光重合開始剤組成の選定がとりわけ重要な理由がここにある。
In the case of using radical polymerization type ultraviolet curable ink in a printed image having such a film thickness difference, polymerization is caused by oxygen dissolved in the ink from the interface between air and ink in the thin film portion of the printed image. It is well known that it is inhibited. Inhibition of polymerization by oxygen occurs on the surface of the printed film, but it is particularly large in thin films. As a measure to mitigate polymerization inhibition, the addition of specific initiators, the increase of polyfunctional monomers, the increase of photopolymerization initiators, the initiation of photons Auxiliary agents are used in combination.
Also, in the thick film portion of the printed image, depending on the photocurable material and photopolymerization initiator in the ink used, the absorption coefficient for ultraviolet rays is large, so most of it is absorbed on the surface of the coating film, and in the film thickness direction. Uniform curing is not performed, and in particular, the coating film strength at a portion far from the coating film surface and close to the substrate may be insufficient.
As described above, the curability of the ultraviolet curable ink is determined by the photocurable material and the photopolymerization initiator to be used. However, in the case of an inkjet recording ink that requires a low viscosity to ensure dischargeability, it is reactive. The use of a polyfunctional monomer having a high viscosity, good curability and high coating strength is suppressed due to its high viscosity, and more than 70% of the monomer is generally formed using a monofunctional or bifunctional monomer. Is. For this reason, for improving the curability, the composition of the photopolymerization initiator has a higher degree of freedom in selection and has a greater influence on the curability. This is why the selection of the photoinitiator composition is particularly important.
また、光重合開始剤は、硬化乾燥した印刷画像の臭気、色再現性に大きな影響を与えるインクの構成材料である。このため、光重合開始剤自体の色と臭気（揮発性）、紫外線照射による光重合開始剤の分解物の色と臭気を考慮した光重合開始剤組成の選定も重要である。特に、印刷物の臭気を小さくすることが必須のラベル、バッケージ、ＣＤ等の印刷用途に対しては、臭気を考慮した光重合開始剤の選定が重要である。 The photopolymerization initiator is a constituent material of ink that greatly affects the odor and color reproducibility of a cured and dried printed image. For this reason, it is also important to select a photopolymerization initiator composition in consideration of the color and odor (volatility) of the photopolymerization initiator itself and the color and odor of the decomposition product of the photopolymerization initiator caused by ultraviolet irradiation. In particular, for printing applications such as labels, packages, and CDs in which it is essential to reduce the odor of the printed matter, it is important to select a photopolymerization initiator in consideration of the odor.
紫外線硬化型インクの硬化性を高めるため、光重合開始剤として２−メチル−１−［４−（メチルチオ）フェニル］―２−モルフォリノプロパン−１―オン（イルガキュア９０７：チバ・スペシャリティ・ケミカルズ製α−アミノケトン系光重合開始剤）とイソプロピルチオキサントンを併用したインクが提案されている（例えば特許文献１、特許文献２、特許文献３参照）。また、光重合開始剤にα−アミノケトン系光重合開始剤とジエチルチオキサントンを併用し、光開始助剤としてアミンを添加したインクが提案されている（例えば特許文献４参照）。さらに特開２００３−２５７０７号公報ではイソプロピルチオキサントンとアミン（光開始助剤）を併用したインクが提案されている（例えば特許文献５参照）。また、表面硬化性の良好な光重合開始剤と内部硬化性の良好な光重合開始剤が併用された例として特許文献として、α−ヒドロキシケトン系開始剤とアシルフォスフィンオキサイド系開始剤を併用したインクが提案されており（例えば特許文献６参照）、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）―ブタノン−１（イルガキュア３６９：チバ・スペシャリティ・ケミカルズ製α−アミノケトン系光重合開始剤）とアシルフォスフィンオキサイド系開始剤を併用したインクが提案されている（例えば特許文献７参照）。また、印刷物の臭気を考慮したインクとして、分解物臭が小さい低臭気の光重合開始剤としてヒドロキシエトキシ基を含有する開始剤（イルガキュア２５２９：チバ・スペシャリティ・ケミカルズ製α−ヒドロキシケトン系光重合開始剤）を用いたインクが提案されている（例えば特許文献８参照）。 In order to enhance the curability of the ultraviolet curable ink, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907: manufactured by Ciba Specialty Chemicals) is used as a photopolymerization initiator. An ink using a combination of an α-aminoketone photopolymerization initiator) and isopropylthioxanthone has been proposed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). In addition, an ink is proposed in which an α-aminoketone photopolymerization initiator and diethylthioxanthone are used in combination with a photopolymerization initiator, and an amine is added as a photoinitiator assistant (see, for example, Patent Document 4). Furthermore, Japanese Patent Application Laid-Open No. 2003-25707 proposes an ink using isopropylthioxanthone and an amine (photoinitiator aid) in combination (for example, see Patent Document 5). In addition, as an example in which a photopolymerization initiator with good surface curability and a photopolymerization initiator with good internal curability are used in combination, an α-hydroxyketone initiator and an acylphosphine oxide initiator are used in combination. (See, for example, Patent Document 6) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369: α-aminoketone manufactured by Ciba Specialty Chemicals) Ink has been proposed in which a photopolymerization initiator) and an acylphosphine oxide initiator are used in combination (for example, see Patent Document 7). In addition, as an ink that takes into account the odor of printed matter, an initiator containing a hydroxyethoxy group as a low-odor photopolymerization initiator having a small decomposition product odor (Irgacure 2529: α-hydroxyketone photopolymerization started by Ciba Specialty Chemicals) An ink using an agent has been proposed (see, for example, Patent Document 8).
しかしながら、光重合開始剤にチオキサントンを用いたインクは、硬化物が黄色に着色するため、プロセスカラー用のシアン色、マゼンタ色のインクに使用した場合、色相が黄味になり、フルカラー印刷物の色再現性領域が狭くなるという問題がある。また、光重合開始剤にイルガキュア９０７を用いたインクは光重合開始剤分解物の臭気が大きいという問題があり、イルガキュア３６９を用いたインクは光重合開始剤分解物が黄色に着色するため、チオキサントンを用いたインクと同様フルカラー印刷物の色再現性領域が狭くなるという問題がある。更に、従来の光重合性開始剤の組み合わせによる紫外線硬化型ジェットインク組成物の薄膜と厚膜での硬化性は、インクジェット記録方式用のインクとして必ずしも満足できるものではなく、光重合開始剤の選定、組み合わせが適切ではなかった。 However, the ink using thioxanthone as the photopolymerization initiator is colored yellow in the cured product, so when used for cyan and magenta inks for process colors, the hue becomes yellow and the color of the full color print There is a problem that the reproducibility region becomes narrow. In addition, the ink using Irgacure 907 as a photopolymerization initiator has a problem that the odor of the photopolymerization initiator decomposition product is large, and the ink using Irgacure 369 is colored yellow because the photopolymerization initiator decomposition product is colored yellow. Similar to the ink using the ink, there is a problem that the color reproducibility region of the full-color printed material becomes narrow. Furthermore, the curability of the ultraviolet curable jet ink composition by the combination of the conventional photopolymerization initiators in the thin film and the thick film is not always satisfactory as the ink for the ink jet recording system, and the selection of the photopolymerization initiator. The combination was not appropriate.
本発明は、印刷画像の領域における低濃度の薄膜部分と高濃度の厚膜部分の双方の硬化性と、被印刷基材への接着性に優れ、印刷画像の臭気が少なく、かつフルカラー印刷物の色再現性に優れた紫外線硬化型プロセスカラージェットインクを提供することを目的とする。 The present invention is excellent in curability of both a low-concentration thin film portion and a high-concentration thick film portion in a printed image area, adhesion to a substrate to be printed, less odor of a printed image, and full-color printed matter. An object of the present invention is to provide an ultraviolet curable process color jet ink having excellent color reproducibility.
本発明者らは、揮発度が低く、硬化乾燥後の印刷画像の臭気が少ない各種の光重合開始剤の組み合わせによる薄膜部分と厚膜部分の硬化性の両立を検討した結果、特定の光重合開始剤と特定の光開始助剤を組み合わせることが有効であることを見いだし本発明に至った。 As a result of examining the coexistence of curability of a thin film portion and a thick film portion by a combination of various photopolymerization initiators having low volatility and low odor of a printed image after curing and drying, specific photopolymerization is performed. The inventors have found that it is effective to combine an initiator and a specific photoinitiator aid, and have reached the present invention.
即ち本発明は、顔料、エチレン性二重結合を有する光重合性化合物、光重合開始剤としてのオキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］―エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］―エチルエステルの混合物、及びアシルフォスフィンオキサイド系化合物、並びに光開始助剤としてアミンを含有することを特徴とする紫外線硬化型インクジェット記録用インク組成物を提供する。
本発明の紫外線硬化型インクジェット記録用インクは、光重合開始剤として、薄膜硬化性の良好なオキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］―エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］―エチルエステルの混合物、及び厚膜硬化性の良好なアシルフォスフィンオキサイド系化合物を併用し、且つ光開始助剤としてアミンを添加し
ているため、印刷画像領域の薄膜部分と厚膜部分の双方での硬化性、及び厚膜部分と被記録材との接着性が良好である。さらにこれら光重合開始剤に含まれる前記混合物及び化合物は低臭気であるため、形成された印刷画像の臭気も小さく抑えることができる。
That is, the present invention relates to a pigment, a photopolymerizable compound having an ethylenic double bond, and oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester as a photopolymerization initiator. And oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, an acylphosphine oxide compound, and an amine as a photoinitiator, an ultraviolet curable ink jet A recording ink composition is provided.
The ultraviolet curable ink jet recording ink of the present invention comprises, as a photopolymerization initiator, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester having good thin film curability. A mixture of oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester and an acyl phosphine oxide compound with good thick film curability are used in combination, and an amine is added as a photoinitiator. Therefore, the curability in both the thin film portion and the thick film portion of the printed image region and the adhesion between the thick film portion and the recording material are good. Furthermore, since the mixture and compound contained in these photopolymerization initiators have a low odor, the odor of the formed printed image can also be kept small.
本発明の紫外線硬化型インクジェット記録用インク組成物は、硬化乾燥した印刷画像の臭気が少なく、低濃度の薄膜部分と高濃度の厚膜部分双方の硬化性、被印刷基材への接着性、フルカラー印刷物の色再現性に優れており、インクジェット記録方法に用いる紫外線硬化型プロセスカラーインク組成物として好適である。 The ink composition for ultraviolet curable ink jet recording of the present invention has less odor of a cured and dried printed image, curability of both a low concentration thin film portion and a high concentration thick film portion, adhesion to a substrate to be printed, It is excellent in color reproducibility of a full-color printed material and is suitable as an ultraviolet curable process color ink composition used in an ink jet recording method.
次に、本発明の実施形態を示すとともに、本発明をさらに詳細に説明する。 Next, while showing embodiment of this invention, this invention is demonstrated still in detail.
本発明で第一の光重合開始剤として使用するオキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］―エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］―エチルエステルの混合物は硬化乾燥後の残存臭気が非常に少ない。また短波長側に主吸収領域を持つため、薄膜硬化性、表面硬化性が良好な開始剤である。しかし、単独で使用した場合、厚膜での硬化性は不十分であり、また、多量に配合すると表面吸収が大きくなりすぎて、特に厚膜形成時における被印刷基材との接着性が低くなる傾向がある。前記混合物を用いた光重合開始剤としてチバ・スペシャリティ・ケミカルズ社製のイルガキュア７５４がある。 Oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2 used as the first photopolymerization initiator in the present invention The mixture of -hydroxy-ethoxy] -ethyl ester has very little residual odor after curing and drying. Moreover, since it has a main absorption region on the short wavelength side, it is an initiator with good thin film curability and surface curability. However, when used alone, the curability with thick films is insufficient, and when blended in a large amount, the surface absorption becomes too large, and the adhesion to the substrate to be printed is particularly low when forming thick films. Tend to be. As a photopolymerization initiator using the mixture, there is Irgacure 754 manufactured by Ciba Specialty Chemicals.
本発明で第二の光重合開始剤として使用するアシルフォスフィンオキサイド系化合物としては、ビス（２，４，６トリメチルベンゾイル）−フェニルフォスフィンオキサイド（チバ・スペチャリティー・ケミカルズ製 商品名：イルガキュア８１９）や、２，４，６トリメチルベンゾイル−ジフェニルフォスフィンオキサイド（ＢＡＳＦ製 諸品名：ルシリンＴＰＯ）が挙げられる。アシルフォスフィンオキサイド系光重合開始剤は長波長側にも吸収領域を持つ広域な吸収特性を有する開始剤であることから、着色剤を高濃度に含む有色のインクに対し好適であり、特に厚膜硬化性（内部硬化性）に優れた開始剤である。しかし、薄膜硬化性および表面硬化性は不十分であり、またエチレン性二重結合を含有する化合物への溶解性も大きくはないため、単独で充分な硬化性を実現する目的でインク中に多量に配合した場合などは、低温保存によりインク中に析出し吐出不良を引き起こす場合がある。 Examples of the acylphosphine oxide compound used as the second photopolymerization initiator in the present invention include bis (2,4,6 trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals). ) And 2,4,6 trimethylbenzoyl-diphenylphosphine oxide (manufactured by BASF, various product names: lucillin TPO). Since the acylphosphine oxide photopolymerization initiator is an initiator having a broad absorption characteristic having an absorption region on the long wavelength side, it is suitable for a colored ink containing a high concentration of a colorant, and particularly thick. It is an initiator excellent in film curability (internal curability). However, the thin film curability and surface curability are insufficient, and the solubility in compounds containing ethylenic double bonds is not large. Therefore, a large amount in the ink for the purpose of achieving sufficient curability alone. In some cases, it may be deposited in ink due to low-temperature storage and cause ejection failure.
本発明で使用する光開始助剤とは、それ自身は紫外線照射により活性化しないが、光重合開始剤と併用すると光重合開始剤単独より開始反応が促進され、硬化反応を効率的に進行させるものである。光開始助剤として使用するアミンは、従来の紫外線硬化型インキ、塗料等に光開始助剤として用いられるものを広く使用することができるが、特に本発明で使用する光開始助剤としてのアミン系化合物としては、第３級アミンが好ましく、例えば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等の脂肪族アミンや、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等の芳香族アミンがあげられる。なお、本発明に使用するアミンとしては、芳香族３級アミンがさらに好ましい。 The photoinitiator used in the present invention is not itself activated by ultraviolet irradiation, but when used in combination with a photopolymerization initiator, the initiation reaction is promoted more than the photopolymerization initiator alone, and the curing reaction proceeds efficiently. Is. The amine used as the photoinitiator aid can be widely used as a photoinitiator aid for conventional UV curable inks, paints, etc., but in particular the amine as the photoinitiator aid used in the present invention. The tertiary compound is preferably a tertiary amine, for example, an aliphatic amine such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, 4-dimethylamino. And aromatic amines such as ethyl benzoate and isoamyl 4-dimethylaminobenzoate. The amine used in the present invention is more preferably an aromatic tertiary amine.
前述した通り、オキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］―エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］―エチルエステルの混合物は、光重合開始剤として用いた場合薄膜硬化性および表面硬化性が良好であるが、厚膜硬化性や被印刷基材との接着性に劣っている。そこで該開始剤を、長波長側に吸収領域を持つ厚膜硬化性（内部硬化性）に優れたアシルフォスフィンオキサイド系化合物を用いた光重合開始剤と併用することにより、薄膜部分、厚膜部分の硬化性のある程度改良されたインクを得ることができる。しかし、低粘度のため酸素による重合禁止作用を受け易い紫外線硬化型インクジェット記録用インク組成物としては、薄膜での硬化性が実用上十分であるとは言えない。
本願発明においては、上記２種類の光重合開始剤を併用し、更に光開始助剤としてアミンを含有させることにより、印刷画像の領域において、低濃度の薄膜部分と高濃度の厚膜部分双方の硬化性と被印刷基材への接着性に優れ、硬化乾燥した印刷画像の臭気が少なく、かつフルカラー印刷物の色再現性に優れたインクを得ることができる。また、芳香族３級アミンの配合量は１〜５質量％が好ましい。１質量％より少ないと硬化性が不十分となる傾向があり、５質量％を越えるとインクの保存安定性の低下、印刷被膜の黄変が発生しやすく、また印刷物の臭気が強くなる傾向がある。
As described above, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester When the mixture is used as a photopolymerization initiator, it has good thin film curability and surface curability, but is inferior in thick film curability and adhesion to a substrate to be printed. Therefore, by using the initiator together with a photopolymerization initiator using an acyl phosphine oxide compound having an absorption region on the long wavelength side and excellent in thick film curability (internal curability), a thin film portion, a thick film An ink having a partially improved curability can be obtained. However, as an ultraviolet curable ink composition for ink jet recording that is susceptible to polymerization inhibition by oxygen due to its low viscosity, it cannot be said that its curability in a thin film is practically sufficient.
In the present invention, by combining the above two types of photopolymerization initiators and further containing an amine as a photoinitiator aid, both the low-concentration thin film portion and the high-concentration thick film portion are included in the printed image area. An ink having excellent curability and adhesion to a substrate to be printed, less odor of a cured and dried printed image, and excellent color reproducibility of a full color print can be obtained. The blending amount of the aromatic tertiary amine is preferably 1 to 5% by mass. If the amount is less than 1% by mass, the curability tends to be insufficient. If the amount exceeds 5% by mass, the storage stability of the ink tends to decrease, the printed film tends to yellow, and the odor of the printed matter tends to increase. is there.
一般に光重合開始剤の含有量が多いほどインクの硬化性は良好となるが、インク粘度の上昇、析出による低温保存安定性の不良などを引き起こす。また、溶解性が良好で、粘度上昇、低温安定性不良を引き起こし難い光重合開始剤であれは、多量に配合できるかもしれないが、未反応の光重合開始剤や、光重合開始剤分解物による、硬化被膜の臭気の増加、硬化被膜強度の低下などの問題が発生する可能性がある。したがって、インク中の光重合開始剤の含有量は５〜１５重量％の範囲で用いることが好ましく、塗膜硬化性を重要視する場合でも、前記含有量範囲において、さらに好ましくは７〜１３質量％の範囲で光重合開始剤の種類とその組み合わせを変えながら、最適の配合を検討することが好ましい。なお、本発明の光重合開始剤組成には、硬化性のさらなる向上等を目的に、さらに他の開始剤を併用することもできる。 In general, the higher the content of the photopolymerization initiator, the better the curability of the ink, but it causes an increase in ink viscosity and poor low-temperature storage stability due to precipitation. In addition, a photopolymerization initiator that has good solubility and hardly causes an increase in viscosity and poor low-temperature stability may be incorporated in a large amount. However, an unreacted photopolymerization initiator or a photopolymerization initiator decomposition product may be used. May cause problems such as an increase in odor of the cured film and a decrease in the strength of the cured film. Therefore, the content of the photopolymerization initiator in the ink is preferably used in the range of 5 to 15% by weight, and even when importance is attached to the coating film curability, the content is more preferably in the range of 7 to 13%. It is preferable to study the optimum blending while changing the type and combination of the photopolymerization initiator in the range of%. The photopolymerization initiator composition of the present invention can be used in combination with another initiator for the purpose of further improving the curability.
本発明の紫外線硬化型インクジェット記録用インク組成物に使用する顔料としては、カーボンブラック、酸化チタン、酸化鉄等の無機顔料、不溶性アゾ顔料、溶性アゾ顔料、フタロシアニン顔料、キナクリドン顔料、ペリレン顔料、イソインドリン顔料、ベンズイミダゾロン顔料、ピランスロン顔料、チオインジゴ顔料、キノフタロン顔料等の有機顔料が挙げられる。顔料のインク中の含有量は、十分な画像濃度、印刷画像の耐光性を得るため、２〜２０質量％の範囲で含有させることが好ましい。 Examples of the pigment used in the ultraviolet curable ink composition for inkjet recording of the present invention include inorganic pigments such as carbon black, titanium oxide and iron oxide, insoluble azo pigments, soluble azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, Examples thereof include organic pigments such as indoline pigments, benzimidazolone pigments, pyranthrone pigments, thioindigo pigments, and quinophthalone pigments. The content of the pigment in the ink is preferably in the range of 2 to 20% by mass in order to obtain a sufficient image density and light resistance of the printed image.
本発明で用いるエチレン性二重結合有する化合物としては、各種の（メタ）アクリレートを用いることができる。具体的には、エチレン性二重結合を１個有する１官能（メタ）アクリレート、エチレン性二重結合を２個以上有する多官能（メタ）アクリレート、（メタ）アクリレ−トオリゴマーが挙げられ、２種類以上併用して用いる事ができる。なお、良好な硬化性を得るためには、エチレン性二重結合を１個有する化合物の含有量は光重合性化合物の総量に対して２０質量％以下とすることが好ましい。さらに（メタ）アクリレートオリゴマーや三官能以上の多感応アクリレートを含有させることが好ましいが、これらは粘度が高く、特に（メタ）アクリレートオリゴマーはモノマーに比較して高粘度であるため、エチレン性二重結合有する化合物の総量に対して、２〜２０質量％の範囲で用いることが好ましい。 Various (meth) acrylates can be used as the compound having an ethylenic double bond used in the present invention. Specific examples include monofunctional (meth) acrylates having one ethylenic double bond, polyfunctional (meth) acrylates having two or more ethylenic double bonds, and (meth) acrylate oligomers. Can be used in combination with more than one type. In order to obtain good curability, the content of the compound having one ethylenic double bond is preferably 20% by mass or less based on the total amount of the photopolymerizable compound. Furthermore, it is preferable to contain a (meth) acrylate oligomer or a trifunctional or higher polyfunctional acrylate, but these have a high viscosity, and in particular, the (meth) acrylate oligomer has a higher viscosity than the monomer. It is preferable to use in the range of 2 to 20% by mass with respect to the total amount of compounds having a bond.
本発明に使用できる１官能（メタ）アクリレートとしては、例えば、メチル、エチル、プロピル、ブチル、アミル、２−エチルヘキシル、イソオクチル、ノニル、ドデシル、ヘキサデシル、オクタデシル、シクロヘキシル、ベンジル、メトキシエチル、ブトキシエチル、フェノキシエチル、ノニルフェノキシエチル、グリシジル、ジメチルアミノエチル、ジエチルアミノエチル、イソボルニル、ジシクロペンタニル、ジシクロペンテニル、ジシクロペンテニロキシエチル等の置換基を有する（メタ）アクリレート等が挙げられる。これらは２種類以上併用して用いることができる。 Examples of the monofunctional (meth) acrylate that can be used in the present invention include methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, And (meth) acrylate having a substituent such as phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl and the like. Two or more of these can be used in combination.
また、多官能（メタ）アクリレートとしては例えば、１，３−ブチレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、１，８−オクタンジオール、１，９−ノナンジオール、トリシクロデカンジメタノール、エチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のジ（メタ）アクリレート、トリス（２−ヒドロキシエチル）イソシアヌレートのジ（メタ）アクリレート、ネオペンチルグリコール１モルに４モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、ビスフェノールＡ１モルに２モルのエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（メタ）アクリレート、トリメチロールプロパン１モルに３モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たトリオールのジまたはトリ（メタ）アクリレート、ビスフェノールＡ１モルに４モル以上のエチレンオキサイドもしくはプロピレンオキサイドを付加して得たジオールのジ（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，ペンタエリスリトールトリ（メタ）アクリレート，ジペンタエリスリトールのポリ（メタ）アクリレート、エチレンオキサイド変性リン酸（メタ）アクリレート、エチレンオキサイド変性アルキルリン酸（メタ）アクリレート等が挙げられる。これらは２種類以上併用して用いることができる。 Examples of the polyfunctional (meth) acrylate include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Di (meth) such as neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, neopentyl glycol , Di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, and triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane. Di or tri (meth) acrylate, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, poly (meth) acrylate of dipentaerythritol, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified alkyl phosphoric acid (meth) acrylate, etc. It is. Two or more of these can be used in combination.
本発明に使用できる（メタ）アクリレートオリゴマーとしては、ウレタン（メタ）アクリレートオリゴマー、エポキシ（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー等が挙げられ、２種類以上併用して用いることができる。 Examples of the (meth) acrylate oligomer that can be used in the present invention include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and the like.
本発明のインクジェット記録用インク組成物には、インクの保存安定性を高めるため、ハイドロキノン、メトキノン、Ｐ−メトキシフェノール、ニトロソアミン塩等の重合禁止剤をインク中に０．０１〜０．５質量％の範囲で添加しても良い。 In the ink composition for ink jet recording of the present invention, a polymerization inhibitor such as hydroquinone, methoquinone, P-methoxyphenol, nitrosamine salt or the like is added in an amount of 0.01 to 0.5% by mass in the ink in order to enhance the storage stability of the ink. You may add in the range.
顔料の分散安定性を高める目的で、本発明のインクジェット記録用インク組成物に用いる分散剤として高分子分散剤を用いること好ましい。
具体的には、味の素ファインテクノ製のアジスパーＰＢ８２１、ＰＢ８２２、ＰＢ８１７、アビシア製のソルスパーズ２４０００ＧＲ、３２０００、楠本化成製のディスパロンＤＡ―７０３―５０、ＤＡ−７０５、ＤＡ−７２５等が挙げられるが、これらに限定されるものではない。また、高分子分散剤の使用量は、顔料に対して１０〜８０質量％の範囲が好ましく、特に２０〜６０質量％の範囲が好ましい。使用量が少なすぎる場合には分散安定性が不十分となり、多すぎる場合にはインクの粘度が高くなり吐出安定性の点から好ましくない。
For the purpose of enhancing the dispersion stability of the pigment, it is preferable to use a polymer dispersant as the dispersant used in the ink composition for ink jet recording of the present invention.
Specific examples include Ajinomoto Fine Techno's Ajisper PB821, PB822, PB817, Avisia's Solsper's 24000GR, 32000, Disparon DA-703-50, DA-705, DA-725 manufactured by Enomoto Kasei. It is not limited to. Further, the amount of the polymer dispersant used is preferably in the range of 10 to 80% by mass, particularly preferably in the range of 20 to 60% by mass with respect to the pigment. When the amount used is too small, the dispersion stability is insufficient, and when it is too large, the viscosity of the ink is increased, which is not preferable from the viewpoint of ejection stability.
また、本発明のインク組成物には、インク吐出を良好に行わせるための表面張力の調整、被印刷基材に対する濡れ性や接着性の付与等を目的に、変性シリコーンオイル等の添加剤や非反応性樹脂等を配合することができる。 In addition, the ink composition of the present invention includes additives such as modified silicone oil for the purpose of adjusting the surface tension for good ink discharge and imparting wettability and adhesiveness to the substrate to be printed. Non-reactive resins and the like can be blended.
本発明の紫外線硬化型ジェットインク組成物の製造は、顔料、（メタ）アクリレート等のエチレン性二重結合を有する化合物を含有し、必要に応じ高分子分散剤、樹脂を加えた混合物をビーズミル等の通常の分散機を用いて顔料を分散した後、光重合開始剤を加え、さらに必要に応じ表面張力調整剤等の添加剤を加えて攪拌、溶解することで調製できる。予め、ビーズミル等の通常の分散機を用いて高濃度の顔料分散液（ミルベース）を作製後、光重合開始剤を溶解した（メタ）アクリレート等のエチレン性二重結合を有する化合物、添加剤等を攪拌、混合して調製することもできる。 The production of the ultraviolet curable jet ink composition of the present invention comprises a compound having an ethylenic double bond such as a pigment and (meth) acrylate, and a mixture containing a polymer dispersant and a resin as necessary, such as a bead mill. After the pigment is dispersed using an ordinary disperser, a photopolymerization initiator is added, and an additive such as a surface tension adjuster is added as necessary, followed by stirring and dissolution. A compound having an ethylenic double bond such as (meth) acrylate in which a photopolymerization initiator is dissolved after preparing a high-concentration pigment dispersion (mill base) using an ordinary dispersing machine such as a bead mill in advance. Can be prepared by stirring and mixing.
以下、実施例により、本発明をさらに詳しく説明する。本発明は、下記実施例によって何ら制限されるものではない。なお、以下実施例中にある部とは、質量部を表す。 Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited by the following examples. In addition, the part in an Example below represents a mass part.
（実施例１）
（高濃度シアン分散液の調整）
ファストゲンブルー５４１２ＳＤ １０部
（大日本インキ化学製フタロシアニン顔料Ｃ．Ｉ．ピグメントブルー１５：３）
高分子分散剤「アジスパーＰＢ８２１」 ３部
ジプロピレングリコールジアクリレート ８７部
を攪拌機で１時間撹拌混合した後、ビーズミルで４時間処理して高濃度シアン分散液を作製した。
Example 1
(Adjustment of high density cyan dispersion)
Fastgen Blue 5412SD 10 parts (Dainippon Ink Chemicals phthalocyanine pigment CI Pigment Blue 15: 3)
Polymer dispersant “Ajisper PB821” 3 parts Dipropylene glycol diacrylate 87 parts was stirred and mixed with a stirrer for 1 hour, and then treated with a bead mill for 4 hours to prepare a high-concentration cyan dispersion.
（シアンインクの調整）
エポキシアクリレートオリゴマー ８部
エチレンオキサイド付加（３モル）トリメチロールプロパントリアクリレート ２８部
ジプロピレングリコールジアクリレート ２８部
イソオクチルアクリレート １６部
ＫＦ−３５１Ａ ０．２部
（信越化学製 ポリエーテルシリコーンオイル）
以上の混合物に、以下の光重合開始剤を加えて６０℃で光重合開始剤を加温溶解した溶液に、前記高濃度シアン分散液を２０部加えて十分に混合後、１．２μｍのメンブランフィルターでろ過することによってジェットプリンター用インクを作製した。
「イルガキュア８１９」 ４部
（チバ・スペシャリティー・ケミカルズ社製）
「イルガキュア７５４」 ４部
（チバ・スペシャリティー・ケミカルズ社製）
ジメチルアミノ安息香酸エチル（日本化薬社製） ３部
(Cyan ink adjustment)
Epoxy acrylate oligomer 8 parts Ethylene oxide addition (3 mol) Trimethylolpropane triacrylate 28 parts Dipropylene glycol diacrylate 28 parts Isooctyl acrylate 16 parts KF-351A 0.2 part (manufactured by Shin-Etsu Chemical Polyether Silicone Oil)
To the above mixture, 20 parts of the high-concentration cyan dispersion was added to a solution prepared by adding the following photopolymerization initiator and heating and dissolving the photopolymerization initiator at 60 ° C., followed by thorough mixing, and then a 1.2 μm membrane. The ink for jet printer was produced by filtering with a filter.
"Irgacure 819" 4 parts (Ciba Specialty Chemicals)
"Irgacure 754" 4 parts (Ciba Specialty Chemicals)
3 parts ethyl dimethylaminobenzoate (Nippon Kayaku Co., Ltd.)
（実施例２〜実施例３、比較例１〜比較例５）
実施例１で用いた光重合開始剤組成に換えて、表．１に示した光重合開始剤の組成及び量を用い、残りの実施例、比較例に対応する紫外線硬化型インクジェット記録用インク組成物を作製した。
作製した紫外線硬化型インクジェット記録用インク組成物について、下記に示す方法で特性を測定し評価を行った。シアンインクに用いた光重合開始剤組成とインク粘度（２５℃）、硬化被膜の臭気、薄膜、厚膜での硬化性、接着性評価結果を示す。なお、インクの粘度、硬化被膜の臭気、インクの硬化性、接着性は下記の方法により評価した。
(Example 2 to Example 3, Comparative Example 1 to Comparative Example 5)
Instead of the photopolymerization initiator composition used in Example 1, a table. Using the composition and amount of the photopolymerization initiator shown in 1, UV-curable ink jet recording ink compositions corresponding to the remaining examples and comparative examples were prepared.
About the produced ultraviolet curable ink composition for inkjet recording, the characteristic was measured and evaluated by the method shown below. The photopolymerization initiator composition used for the cyan ink, the ink viscosity (25 ° C.), the odor of the cured film, the curability of the thin film and the thick film, and the evaluation results of the adhesion are shown. Ink viscosity, cured coating odor, ink curability and adhesion were evaluated by the following methods.
［粘度測定方法］
Ｅ型粘度計により各実施例、比較例で作製したインクの２５℃での粘度を測定した。
[Viscosity measurement method]
The viscosity at 25 ° C. of the inks prepared in each Example and Comparative Example was measured with an E-type viscometer.
［薄膜硬化性評価方法］
各実施例、比較例で作製したインクをポリカーボネート板（旭硝子製 商品名：レキサン）にインクを約２μｍの厚みとなるようにスピンコータで塗布し、コンベア式紫外線照射装置（日本電池製メタルハライドランプ１灯：出力１２０Ｗ／ｃｍ）により、照射エネルギー０．２ｊ／ｃｍ２で紫外線を照射し、不織布（旭化成製 商品名：ベンコット）による擦り試験で表面に傷がつかなくなるパス回数を評価した。
[Thin film curability evaluation method]
The ink prepared in each example and comparative example was applied to a polycarbonate plate (trade name: Lexan, manufactured by Asahi Glass) with a spin coater so that the ink had a thickness of about 2 μm, and a conveyor type ultraviolet irradiation device (one metal halide lamp manufactured by Nippon Batteries) : Output 120 W / cm), ultraviolet rays were irradiated at an irradiation energy of 0.2 j / cm 2, and the number of passes at which the surface was not damaged was evaluated by a rubbing test using a nonwoven fabric (trade name: Bencott manufactured by Asahi Kasei).
［厚膜硬化性評価方法］
各実施例、比較例で作製したインクを、ポリカーボネート板（旭硝子製 商品名：レキサン）にインクを約６μｍの厚みとなるようにスピンコータで塗布し、コンベア式紫外線照射装置（日本電池製メタルハライドランプ１灯：出力１２０Ｗ／ｃｍ）により、照射エネルギー０．２ｊ／ｃｍ２で紫外線を照射し、不織布（旭化成製 商品名：ベンコット）による擦り試験で表面に傷がつかなくなるパス回数を評価した。
[Thick film curability evaluation method]
The ink produced in each example and comparative example was applied to a polycarbonate plate (trade name: Lexan, manufactured by Asahi Glass) with a spin coater so that the ink had a thickness of about 6 μm, and a conveyor type ultraviolet irradiation device (metal halide lamp 1 manufactured by Nippon Batteries). The number of passes at which the surface was not damaged by a rubbing test using a non-woven fabric (trade name: Bencott manufactured by Asahi Kasei) was evaluated.
［接着性評価方法］
カッターを用いて、ポリカーボネート板上（旭硝子製 商品名：レキサン）に６μｍの厚さで実施例１〜３、比較例１〜５で作成したインクを塗布し、塗膜面をクロス状にカットし、カットした部分に粘着テープ（ニチバン製）を約１ｋｇ重の力で指で押しつけながら５０回擦って貼り、これを引き剥がすことによる塗膜の剥離状態を目視で評価した。
○：剥離しない。
△：一部剥離する。
×；完全に剥離する。
[Adhesion evaluation method]
Using a cutter, the ink created in Examples 1 to 3 and Comparative Examples 1 to 5 was applied in a thickness of 6 μm onto a polycarbonate plate (trade name: Lexan manufactured by Asahi Glass Co., Ltd.), and the coating surface was cut into a cloth shape. Then, an adhesive tape (manufactured by Nichiban) was applied to the cut portion by rubbing 50 times while pressing it with a finger with a force of about 1 kg, and the peeled state of the coating film was visually evaluated.
○: Does not peel.
Δ: Partially peeled off.
X: Completely peeled off.
［硬化被膜の臭気の評価方法］
厚膜硬化性評価後の硬化被膜の臭気を５人で感応評価し、臭気の強いさを３段階区分してそれぞれ３点、２点、１点をつけ、合計点によって以下のように臭気「大」、「中」、「小」に分類した。
（評価基準）
臭気「大」 １５点〜１２点
臭気「中」 １１点〜８点
臭気「小」 ５点〜７点
[Method for evaluating odor of cured film]
The odor of the cured film after the thick film curable evaluation was sensitively evaluated by 5 people, and the odor intensity was classified into 3 levels, giving 3 points, 2 points, and 1 point, respectively. Classified as "Large", "Medium" and "Small".
(Evaluation criteria)
Odor "Large" 15 to 12 points Odor "Medium" 11 to 8 points Odor "Small" 5 to 7 points
（表１） (Table 1)
略称で示した表中の開始剤の物質名及び製造メーカー名は以下の通りである。
Ｉｒｇ．８１９（イルガキュア８１９）：チバ・スペシャリティ・ケミカルズ製
ビス（２，４，６トリメチルベンゾイル）−フェニルフォスフィンオキサイド
Ｉｒｇ．７５４（イルガキュア７５４）：チバ・スペシャリティ・ケミカルズ製
オキシ−フェニル−アセチックアシッド２−［２−オキソ−２−フェニル−アセトキシ−エトキシ］―エチルエステルとオキシ−フェニル−アセチックアシッド２−［２−ヒドロキシ−エトキシ］―エチルエステルの混合物
ＥＰＡ ：日本化薬製 ジメチルアミノ安息香酸エチル
Ｉｒｇ．１２７（イルガキュア３６８）：チバ・スペシャリティ・ケミカルズ製
２−ヒドロキシ−１−｛−４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパン−１−オン
Ｉｒｇ．２９５９（イルガキュア２９５９）：チバ・スペシャリティ・ケミカルズ製
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
The substance names and manufacturer names of the initiators in the abbreviated table are as follows.
Irg. 819 (Irgacure 819): Bis (2,4,6 trimethylbenzoyl) -phenylphosphine oxide Irg. Manufactured by Ciba Specialty Chemicals. 754 (Irgacure 754): oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and oxy-phenyl-acetic acid 2- [2- manufactured by Ciba Specialty Chemicals Hydroxy-ethoxy] -ethyl ester mixture EPA: Nippon Kayaku Co., Ltd. Ethyl dimethylaminobenzoate Irg. 127 (Irgacure 368): 2-hydroxy-1-{-4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1 manufactured by Ciba Specialty Chemicals -On Irg. 2959 (Irgacure 2959): 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one manufactured by Ciba Specialty Chemicals
上記の通り、実施例１、２、３のインクは、硬化被膜の臭気が小さく、薄膜硬化性、厚膜硬化性、厚膜硬化被膜の接着性が共に良好であった。これに対し、比較例１と比較例３のインクは低粘度で薄膜硬化性は良好であるが、厚膜硬化性、あるいは厚膜硬化被膜の接着性が不良である。比較例２のインクは厚膜硬化性、厚膜硬化被膜の接着性は比較例１、比較例３と比べて良好であるが、薄膜硬化性が不良である。また、低臭気のα−ヒドロキシケトン系開始剤として、イルガキュア１２７、イルガキュア２５２９を使用した比較例４と比較例５のインクは薄膜硬化性は良好であるが、粘度が高くなり、厚膜硬化被膜の接着性が不良であった。また双方の光重合開始剤ともに溶解性が必ずしも十分ではなく、常温で液体状態のイルガキュア７５４と比較して、溶解安定性に劣っており、インク中に多量に使用したときは、特に低温で保存、駆動したときに析出物がノズルに詰まって吐出不良を起こす危険性が大きくなる。また、従来技術において記載したように、酸素阻害を受け難く薄膜硬化性の良好なα―アミノアセトフエノン系開始剤の中で揮発度の小さいイルガキュア３６９、イルガキュア９０７を主成分として用いたI光重合開始剤は、それぞれ分解物の着色（黄変）、臭気の点で問題があることがｗかっているため、実施例、比較例には最初から採用していない。
As described above, the inks of Examples 1, 2, and 3 had a small cured film odor, and had good thin film curability, thick film curability, and thick film cured film adhesiveness. In contrast, the inks of Comparative Example 1 and Comparative Example 3 have low viscosity and good thin film curability, but thick film curability or adhesion of the thick film cured film is poor. The ink of Comparative Example 2 has better thick film curability and better adhesion of the thick film cured film than Comparative Examples 1 and 3, but the thin film curability is poor. The inks of Comparative Example 4 and Comparative Example 5 using Irgacure 127 and Irgacure 2529 as low odor α-hydroxyketone initiators have good thin film curability, but have a high viscosity and thick film cured coating. The adhesion was poor. In addition, both photopolymerization initiators are not necessarily sufficiently soluble, have poor solubility stability compared to Irgacure 754 in a liquid state at room temperature, and are stored at a low temperature, especially when used in large amounts in ink. When driven, the risk of deposits clogging the nozzle and causing defective discharge increases. In addition, as described in the prior art, I-light using Irgacure 369 and Irgacure 907, which have low volatility among α-aminoacetophenone initiators that are less susceptible to oxygen inhibition and have good thin film curability, as main components. Since the polymerization initiators have problems in terms of coloring (yellowing) and odor of the decomposed products, they are not employed from the beginning in the examples and comparative examples.
Claims (2)
The ink composition for ultraviolet curable ink jet recording according to claim 1, wherein the amine is an aromatic tertiary amine and the content in the ink composition is 1 to 5 mass%.
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Cited By (10)
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|---|---|---|---|---|
| JP2010112073A (en) * | 2008-11-06 | 2010-05-20 | Seiren Co Ltd | Building plate |
| JP2010138315A (en) * | 2008-12-12 | 2010-06-24 | Seiko Epson Corp | Ink set, inkjet printing apparatus and inkjet recording method |
| CN102753630A (en) * | 2010-09-24 | 2012-10-24 | 积水化学工业株式会社 | Curable composition for inkjet and method for producing electronic component |
| JP2013014740A (en) * | 2011-06-10 | 2013-01-24 | Jnc Corp | Photocurable inkjet ink |
| US10308824B2 (en) | 2016-02-12 | 2019-06-04 | Seiko Epson Corporation | Radiation curable ink jet composition and ink jet recording method |
| US10934444B2 (en) | 2018-09-27 | 2021-03-02 | Seiko Epson Corporation | Radiation-curable ink jet composition and ink jet recording method |
| JP2022519821A (en) * | 2019-01-24 | 2022-03-25 | アグフア－ゲヴエルト，ナームローゼ・フエンノートシヤツプ | Radiation-curable ink for the manufacture of printed circuit boards Jet ink |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005076074A2 (en) * | 2004-02-02 | 2005-08-18 | Ciba Specialty Chemicals Holding Inc. | Functionalized photoinitiators |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005076074A2 (en) * | 2004-02-02 | 2005-08-18 | Ciba Specialty Chemicals Holding Inc. | Functionalized photoinitiators |
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| JP2010112073A (en) * | 2008-11-06 | 2010-05-20 | Seiren Co Ltd | Building plate |
| JP2010138315A (en) * | 2008-12-12 | 2010-06-24 | Seiko Epson Corp | Ink set, inkjet printing apparatus and inkjet recording method |
| CN102753630A (en) * | 2010-09-24 | 2012-10-24 | 积水化学工业株式会社 | Curable composition for inkjet and method for producing electronic component |
| JP2013014740A (en) * | 2011-06-10 | 2013-01-24 | Jnc Corp | Photocurable inkjet ink |
| US10308824B2 (en) | 2016-02-12 | 2019-06-04 | Seiko Epson Corporation | Radiation curable ink jet composition and ink jet recording method |
| US10934444B2 (en) | 2018-09-27 | 2021-03-02 | Seiko Epson Corporation | Radiation-curable ink jet composition and ink jet recording method |
| JP2022519821A (en) * | 2019-01-24 | 2022-03-25 | アグフア－ゲヴエルト，ナームローゼ・フエンノートシヤツプ | Radiation-curable ink for the manufacture of printed circuit boards Jet ink |
| US11981823B2 (en) | 2019-06-17 | 2024-05-14 | Seiko Epson Corporation | Radiation-curable ink jet composition and ink jet method |
| US11884828B2 (en) | 2020-03-25 | 2024-01-30 | Seiko Epson Corporation | Radiation curable ink jet composition and ink jet method |
| US11987715B2 (en) | 2020-03-25 | 2024-05-21 | Seiko Epson Corporation | Radiation curable ink jet composition and ink jet method |
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