JPS58149969A - Energetic ray curing printing ink composition - Google Patents
Energetic ray curing printing ink compositionInfo
- Publication number
- JPS58149969A JPS58149969A JP57031787A JP3178782A JPS58149969A JP S58149969 A JPS58149969 A JP S58149969A JP 57031787 A JP57031787 A JP 57031787A JP 3178782 A JP3178782 A JP 3178782A JP S58149969 A JPS58149969 A JP S58149969A
- Authority
- JP
- Japan
- Prior art keywords
- printing ink
- acid
- epoxy
- ink composition
- reaction product
- 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
- 238000007639 printing Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title claims description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 150000002763 monocarboxylic acids Chemical class 0.000 claims abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229930185605 Bisphenol Natural products 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical group 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 11
- 229920000647 polyepoxide Polymers 0.000 abstract description 11
- -1 acrylic ester Chemical class 0.000 abstract description 10
- 238000007645 offset printing Methods 0.000 abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 abstract description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007870 radical polymerization initiator Substances 0.000 abstract description 4
- 244000028419 Styrax benzoin Species 0.000 abstract description 3
- 235000000126 Styrax benzoin Nutrition 0.000 abstract description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 abstract description 3
- 229960002130 benzoin Drugs 0.000 abstract description 3
- 235000019382 gum benzoic Nutrition 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 16
- 239000000976 ink Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920000180 alkyd Polymers 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Chemical class O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Chemical class OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-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
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- FMNWHPUEOOSFHG-UHFFFAOYSA-N 2-chloro-2-hydroxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Cl)(O)C(=O)C1=CC=CC=C1 FMNWHPUEOOSFHG-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-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
- VSKXJRZPVDLHFY-UHFFFAOYSA-N 2-methylcyclohexane-1-carboxylic acid Chemical compound CC1CCCCC1C(O)=O VSKXJRZPVDLHFY-UHFFFAOYSA-N 0.000 description 1
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 244000301850 Cupressus sempervirens Species 0.000 description 1
- SBOBXVGDOAOGKL-UHFFFAOYSA-N Eleostearin Natural products CCCCC=CC=CC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CC=CC=CCCCC)COC(=O)CCCCCCCC=CC=CC=CCCCC SBOBXVGDOAOGKL-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000002250 progressing effect Effects 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
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 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
Landscapes
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は活性エネルギー線硬化性印刷インキ組成物に関
するものであり、詳り、 <は紫外線もシ、〈は電子線
等の照射により極めて短時間に硬化り、、L、かも基材
への密着性および折りまげ性等のhロエ性に優れ、さら
にオフセットインキに用いた場合にはオフセット印刷適
正に優れた硬化性印刷インキ組成に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an active energy ray-curable printing ink composition. The present invention relates to a curable printing ink composition which has excellent adhesion to a substrate and excellent properties such as foldability, and is also suitable for offset printing when used in an offset ink.
近年、活性エネルギー線による硬化性組成物の研究はさ
かんにおこなわれており、その中でも印刷インキ等の分
野では実用化が進められている。これらはラジカル重合
性を有するプレポリマーおよびモノマーと、必要に応じ
てラジカル重合開始剤からなっており、プレポリマーと
し、ではアルキッドアクリレート、ポリエステルアクリ
レート、エポキシアクリレート、ウレタン変性ケクリレ
ート等が、またモノマーとし、では、脂肪族アルコール
のアクリレート、フェノール性水酸基のアルキレンオキ
サイド付加体アクリレート、グリシジル化合物のアクリ
レート等が用いられていた。In recent years, research on compositions curable by active energy rays has been actively conducted, and among these, practical application is progressing in fields such as printing inks. These are composed of prepolymers and monomers having radical polymerizability, and radical polymerization initiators as necessary.The prepolymers are alkyd acrylates, polyester acrylates, epoxy acrylates, urethane-modified quecrylates, etc., and the monomers are In this case, acrylates of aliphatic alcohols, acrylates of alkylene oxide adducts of phenolic hydroxyl groups, acrylates of glycidyl compounds, etc. were used.
アルキッドアクリレートは〜樹脂酸により可塑化され、
硬化皮膜が軟化され、耐溶剤性に劣る。Alkyd acrylates are plasticized by resin acids,
The cured film is softened and has poor solvent resistance.
エポキシアクリレートは硬化性に優れているが、接着性
に劣り、また、オフセット印刷インキに用いた場合には
、アミ点再現性等のオフセット印刷適性に劣る欠点を有
し、ている。また、脂肪酸変性アルキッドのポリイソシ
アネート媒体によるアクリレートは、分子中のウレタン
結合が原因で高粘度化するため作業性が悪く、粘度を低
下させる際に、反応性希釈剤の七ツマ−の使用割合が増
し1、硬化性が劣化する欠点を有している。Although epoxy acrylate has excellent curability, it has poor adhesive properties, and when used in offset printing inks, it has the disadvantage of poor offset printing suitability such as dot reproducibility. In addition, acrylate using a polyisocyanate medium of fatty acid-modified alkyd has poor workability because it becomes highly viscous due to the urethane bonds in the molecule. Addition 1: It has the disadvantage of deteriorating curability.
このように、これ等の活性エネルギー線硬化性組成物を
印刷インキ用組成物として使用する場合、対象とする金
属素材および各種有機皮膜塗装板等の種類によっては密
着性が不十分であったり、また折り曲げ性、打抜き性等
の耐加工性に問題があり、さらにオフセット印刷適性に
劣るため、必ずしも十分に実用に耐えるものは少なかっ
た。As described above, when these active energy ray-curable compositions are used as printing ink compositions, the adhesion may be insufficient depending on the target metal material and the type of various organic coating coated boards. In addition, there were problems with processing resistance such as bendability and punching properties, and furthermore, the suitability for offset printing was poor, so there were few products that could be used satisfactorily.
本発明は、これらの欠点を改良すべく鋭意研究の結果硬
化性に優れ、かつ基材への密着性、折り曲げ性等の耐加
工性妃優れた、活性エネルギ線硬化性印刷インキ組成物
を発明するに至った。As a result of intensive research to improve these drawbacks, the present invention has invented an active energy beam-curable printing ink composition that has excellent curability and excellent processing resistance such as adhesion to substrates and bendability. I ended up doing it.
すなわち本発明は、
(a)1分子当りエポキシ基を1個以上有するエポキシ
化合物とラジカル重合性を有しないモノカルボン酸との
反応生成物
示されるアクリル酸もし、〈はメタクリル酸エステル系
モノマー
(ただし、一般式(1)においてRtは水素原子、メチ
ル基、エチル基、プロピル基もし、〈はブチル基を、R
2は水素原子もし、〈はメチル基を、Xはベンゼン環、
アルギルベンゼン環モL、 <’はビスフェノール残基
を、nは1〜10の整数を、yは1〜4の整数を示す。That is, the present invention is directed to (a) a reaction product of an epoxy compound having one or more epoxy groups per molecule and a monocarboxylic acid that does not have radical polymerizability; , In general formula (1), Rt is a hydrogen atom, methyl group, ethyl group, propyl group, < is a butyl group, R
2 is a hydrogen atom, < is a methyl group, X is a benzene ring,
Argylbenzene ring moL, <' represents a bisphenol residue, n represents an integer of 1 to 10, and y represents an integer of 1 to 4.
)
本発明において、エポキシ化合物とは、1分子中にエポ
キシ基を1個以上、望まし、〈は1.5個以上有すれば
良く、グリシジルエーテル型エポキシ樹脂、グリシジル
エステル型エポキシ樹脂、グリシジルアミン型エポキシ
衝脂、線状脂肪族エポキサイド脂環型エポキシ樹脂等を
好適に使用すZことができる。グリシジルエーテル型エ
ポキシ机脂としては、ビスフェノールAジグリシジルエ
ーテル、ビスフェノールAジ−βメチルグリシジルエー
テル、ビスフェノールFジグリシジルエーテル、水添加
ビスフェノールAグリシジルエーテル、ビスフェノール
Aアルキレンオキサイド付加物のジグリシジルエーテル
、ノボラックグリシジルエーテル、ポリアルキレングリ
コールジグリシジルエーテル、エポキシウレタン樹脂等
があり、グリシジルエステル型エポキシ樹脂としてはフ
タル酸ジグリシジルエステル、ダイマー酸ジグリシジル
エステル等があり、グリシジルアミン型エポキシ樹脂と
してはトリグリシジルイソシアヌレート等があシ、また
線状脂肪族エポキシ樹脂としては、エポキシ化ポリブタ
ジェン、エポキシ化大豆油等力”あり、脂環族エポキシ
樹脂としては、ビス(3,4−エポキシ−6−メチルシ
クロヘキシルメチル)アシヘ−)、3.4−エポキシ−
6−メチルシクロヘキシルメチル、3,4−エポキシ−
6−メチルシクロヘキサンカルボキシレート等を挙げる
ことができる。) In the present invention, the epoxy compound means one or more epoxy groups in one molecule, preferably 1.5 or more, and includes glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine. Type epoxy resin, linear aliphatic epoxide, alicyclic epoxy resin, etc. can be suitably used. Glycidyl ether type epoxy fats include bisphenol A diglycidyl ether, bisphenol A di-β methyl glycidyl ether, bisphenol F diglycidyl ether, water-added bisphenol A glycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, and novolak glycidyl. There are ethers, polyalkylene glycol diglycidyl ethers, epoxy urethane resins, etc. Glycidyl ester type epoxy resins include phthalic acid diglycidyl ester and dimer acid diglycidyl ester, etc. Glycidylamine type epoxy resins include triglycidyl isocyanurate etc. In addition, linear aliphatic epoxy resins include epoxidized polybutadiene and epoxidized soybean oil, and alicyclic epoxy resins include bis(3,4-epoxy-6-methylcyclohexylmethyl) acyl. -), 3.4-epoxy-
6-methylcyclohexylmethyl, 3,4-epoxy-
Examples include 6-methylcyclohexanecarboxylate.
ラジカル重合性を有しないモノカルボン酸とはギ酸、酢
酸、プロピオン酸、カプロン酸、カプリル酸、ラウリン
酸、ステアリン酸等の脂肪族飽和−塩基酸、オレイン酸
、リノール酸、リルン酸、エレオステアリン酸等の不飽
和−塩基酸、脱水ヒマシ油脂肪酸、アマニ油脂肪酸、大
豆油脂肪酸、トール油脂肪酸、ヒマシ油脂肪酸等の脂肪
酸、ロジン、水添加ロジン等ロジン誘導体、安息香酸、
t−ブチル安息香酸等の芳香族−塩基酸等を使用するこ
とができる。Monocarboxylic acids that do not have radical polymerizability include aliphatic saturated basic acids such as formic acid, acetic acid, propionic acid, caproic acid, caprylic acid, lauric acid, and stearic acid, oleic acid, linoleic acid, lylunic acid, and eleostearin. Unsaturated basic acids such as acids, fatty acids such as dehydrated castor oil fatty acids, linseed oil fatty acids, soybean oil fatty acids, tall oil fatty acids, castor oil fatty acids, rosin, rosin derivatives such as water-added rosin, benzoic acid,
Aromatic-basic acids such as t-butylbenzoic acid can be used.
エポキシ化合物とラジカル重合性を有しないモノカルボ
ン酸の反応は、70°C〜300°Cの範囲で、不活性
ガス気流下でおこなうことができ、エポキシ基l当量に
対し、カルボキシル基0.5当量以上反応させることが
好ましいが、さらに好ましくはエポキシ基のカルボキシ
ル基との反応により生じた2級のOH基に対してもエス
テル化させることがオフセット印刷インキに用いる場合
には好触媒を用いることもできる。触媒としては、エポ
キシ基の開環反応においてはアミ・ン触媒を用いる20
0〜300°Cの高温で行なうか、酸触媒を用い200
以下で行なうこともできる。必要に応じて反応溶媒を用
い、反応により生ずる水を除去および反応−の焦けつき
を防止することができる。The reaction between an epoxy compound and a monocarboxylic acid that does not have radical polymerizability can be carried out in the range of 70°C to 300°C under an inert gas flow, and 0.5 carboxyl groups per 1 equivalent of epoxy groups. It is preferable to react in an equivalent amount or more, and more preferably to also esterify the secondary OH group generated by the reaction of the epoxy group with the carboxyl group. When used in offset printing ink, a good catalyst is used. You can also do it. As a catalyst, an amine catalyst is used in the ring-opening reaction of epoxy groups20
It can be carried out at a high temperature of 0 to 300°C or 200°C using an acid catalyst.
You can also do it below. If necessary, a reaction solvent can be used to remove water produced by the reaction and to prevent the reaction from burning.
一般式(1)で示される化合物はアクリル酸もしくはメ
タクリル酸エステル系モノマーであり、フェノール、ア
ルキルフェノール、レゾルシン、ビスフェノール等のフ
ェノールにエチレンオキサイド、プロピレンオキサイド
等のアルキレンオキサイドを付加し、アクリル酸もしく
はメタクリル酸をエステル化することによって得られる
(メタ)アクリル酸エステル系モノマーである。The compound represented by the general formula (1) is an acrylic acid or methacrylic acid ester monomer, which is obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a phenol such as phenol, alkylphenol, resorcinol, or bisphenol. It is a (meth)acrylic acid ester monomer obtained by esterifying.
本発明において、活性エネルギー線が紫外線である場合
には、光増感剤(ラジカル重合開始剤)を添加する必豪
があり、ベンゾイン、ベンゾインメチルエーテル、ベン
ゾインエチルエーテル、ベンゾインイソプロピルエーテ
ル、α−クロロベンゾイン、a−アリルベンゾイン等の
ベンゾイン系増感剤、ベンゾフェノン、P−メチルペン
ソフエ/7、P−pクロベンゾフエノン、0−ベンソイ
ル安息香酸メチル、アセトフェノン等のアリールケトン
系増感剤、4.4′−ビスジエ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等のジアルキルアミノアリー
ルケトン系増感剤、チオキサントン、キサントンおよび
そのハロゲン置換体等の多積カルボニル系増感剤があげ
られ、これらの単独もしくは適宜組み合せにより用いる
こともできる。これらの光増感剤は組成物中に0〜30
重量%の範囲で用いることができるが、好ましくは0〜
15重量%の範囲であることが望ましい。In the present invention, when the active energy ray is ultraviolet rays, it is necessary to add a photosensitizer (radical polymerization initiator), such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-chloro Benzoin sensitizers such as benzoin and a-allylbenzoin; aryl ketone sensitizers such as benzophenone, P-methylpensophe/7, P-p clobenzophenone, methyl 0-benzoylbenzoate, and acetophenone; 4 .Dialkylaminoarylketone sensitizers such as 4'-bisdiethylaminobenzophenone, isoamyl P-dimethylaminobenzoate, and P-dimethylaminoacetophenone, and multicarbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products. These can be used alone or in appropriate combinations. These photosensitizers may be present in the composition in amounts ranging from 0 to 30
It can be used in a range of weight%, but preferably 0 to
A range of 15% by weight is desirable.
本発明に−おいて、(a)と(b)との配合割合は特に
制限されるものではないが、好ましくは←)10〜80
重量%、(b)20〜90重量%となるような配合割合
である。In the present invention, the blending ratio of (a) and (b) is not particularly limited, but is preferably ←) 10-80
(b) The blending ratio is 20 to 90% by weight.
(a)のエポキシ化合物の分子量が200より低いもの
を用いると、得られた(a)の反応生成物の粘度が低く
なるため、(b)のモノマーの使用量が減や、硬化皮膜
強度が弱くカってしまう。また、分子量が4000を超
えるもの管用いると得られた(a)の反応生成物の粘度
が高くなり、従って(b)のモノマーの使用量が増加し
、その為架橋密度があがり、接着性、加工性において劣
化が見られ好ましくない。If an epoxy compound (a) with a molecular weight lower than 200 is used, the viscosity of the resulting reaction product (a) will be low, so the amount of monomer (b) used will be reduced, and the strength of the cured film will be reduced. I get weak and angry. In addition, if a tube with a molecular weight exceeding 4000 is used, the viscosity of the reaction product obtained in (a) will increase, and therefore the amount of monomer (b) used will increase, resulting in an increase in crosslinking density and poor adhesiveness. Deterioration in workability is observed, which is not preferable.
エポキシ化合物として前記のものが使用できるが、特に
加工性を良くする為にはビスフェノールタイプエポキシ
化合物を使用することが好ましく、また、オフセット印
刷適性を重視する場合にはノボラックタイプエポキシ化
合物を使用することが好ましい。従りて要求される品質
により両者の使用割合をかえ、用いることができる。The above-mentioned epoxy compounds can be used, but it is preferable to use bisphenol type epoxy compounds to particularly improve processability, and novolac type epoxy compounds are used when suitability for offset printing is important. is preferred. Therefore, the ratio of both can be changed depending on the quality required.
成分(a)のエポキシ化合物とラジカル重合性を肩しな
いモノカルボン酸との反応生成物の軟化点が120°C
以上の場合には、使用する(b)のモノマーが大量に入
り、加工性が劣化する。また、(a)の反応生成物を(
b)のモノマーで希釈フェノとする胸倉に、ゲル化がお
こり目的とする硬化性反覆組成物である希釈フェノを得
ることができない。The softening point of the reaction product between the epoxy compound of component (a) and the monocarboxylic acid that does not have radical polymerizability is 120°C.
In the above case, a large amount of monomer (b) is used, and processability deteriorates. In addition, the reaction product of (a) is (
Gelation occurs in the diluted pheno with the monomer b), making it impossible to obtain the desired diluted pheno, which is a curable repeating composition.
さらに、本発明においては必賛に応じてTi機もしくは
無機顔料、体質顔料、可塑剤、各1[檎脂類、有憧溶剤
、硬化促進用助剤、消泡剤、界面活性剤等を添加するこ
とができる。また、本発明の効果ヲ1泪害しない範囲で
徊のモノマーやプレポリマーを併用することもできる。In addition, in the present invention, Ti organic or inorganic pigments, extender pigments, plasticizers, 1 each of each [cypress fat, solvents, curing accelerators, antifoaming agents, surfactants, etc. are added. can do. In addition, other monomers and prepolymers may be used in combination without detracting from the effects of the present invention.
以下具体9−1により本発明を説明する。例中の鄭は全
てtf#部を示す。The present invention will be explained below using Example 9-1. All symbols in the example indicate the tf# part.
製造例−1
エピコー)1001 (シェル化学■製ビスフェノール
Aタイプエポキシ樹脂、分子1i900)470部、オ
レイン酸530部、キシレン10部を攪拌機、分離管直
結コンデンサー付4つロフラスコに仕込み、N11
ガスを吹き込みながら200〜220°Cにて7時間反
応し、酸価が6.0になったら、キシレンを回収し、樹
脂(A)を得た。Production Example-1 470 parts of Epicor) 1001 (Bisphenol A type epoxy resin manufactured by Shell Chemical ■, Molecule 1i900), 530 parts of oleic acid, and 10 parts of xylene were charged into four Lof flasks equipped with a stirrer and a condenser directly connected to the separation tube, and N11
The reaction was carried out at 200 to 220° C. for 7 hours while blowing gas, and when the acid value reached 6.0, xylene was recovered to obtain resin (A).
樹脂(A)のダイア七トンアルコール50%希釈粘りた
。(以後樹脂粘度はこの方法により測定表示する。)
製造例2
エビコー)1004(シェル化学t14 gビスフェノ
ールA41イブエポキシ樹脂分子童1600)450部
、P−Z−%+9−プfk安息香al−2,5、,9部
、キシレン10部1製造例−1と同様に200〜220
°Cにて8時間反応させ、酸価が7.0になったらキシ
レンを回収し、輌脂(B)を得た。樹脂(B)の粘度は
Yであった。また、軟化点はキャピラリー法にて測定し
たところ、78°Cでめった。The resin (A) was diluted with 50% diluted alcohol. (Hereafter, the resin viscosity will be measured and displayed using this method.) Production Example 2 Ebicor) 1004 (Shell Chemical T14g Bisphenol A41 Eve Epoxy Resin Molecule 1600) 450 parts, P-Z-% + 9-Pfk Benzoic Al-2, 5, 9 parts, xylene 10 parts 1 200 to 220 as in Production Example-1
The reaction was carried out at °C for 8 hours, and when the acid value reached 7.0, xylene was collected to obtain rosin (B). The viscosity of the resin (B) was Y. Further, the softening point was measured by a capillary method and was found to be 78°C.
製造(7112
DEN431 (ダウ・ケミカル■裏ノボラツクタイプ
エボキシ便脂、分子量760)183部、オレイン酸2
90部、安息香酸230部、キシレン10部、トリエチ
レンジアミン0.7部を製造例1と同様に仕込み、11
gガスを吹きこみながら170〜190°Cにて4時間
反応させ酸価4に々ったら、キシレン金回収し、樹脂(
c)を得た。樹脂(clは粘度Eでめった。Manufacture (7112 DEN431 (Dow Chemical ■ back novolac type eboxy stool fat, molecular weight 760) 183 parts, oleic acid 2
90 parts of benzoic acid, 230 parts of benzoic acid, 10 parts of xylene, and 0.7 parts of triethylenediamine were charged in the same manner as in Production Example 1.
The reaction was carried out at 170 to 190°C for 4 hours while blowing g gas into it, and when the acid value reached 4, the xylene gold was recovered and the resin (
c) was obtained. Resin (Cl was measured at viscosity E.
製造例4
アデカサイザー〇−130F(旭電化株製エポキシ化大
豆油、分子量980)210部、水添 ロジン440部
、カプロン@!50g、キシレン101ut製造例1と
同様に仕込み200〜220°Cにて7時間反応させ、
酸価5.0になったらキシレンを回収し、樹Aft (
D)を得た。粘度はGでめった。Production Example 4 210 parts of ADEKASIZER 〇-130F (Epoxidized soybean oil manufactured by Asahi Denka Co., Ltd., molecular weight 980), 440 parts of hydrogenated rosin, Kapro@! 50 g, 101 ut of xylene were prepared in the same manner as in Production Example 1, and reacted at 200 to 220°C for 7 hours.
When the acid value reaches 5.0, the xylene is collected and the tree Aft (
D) was obtained. The viscosity was measured at G.
製造例5
エピコート828 (シェル化学製ビスフェノールタイ
プエポキシ樹脂、分子t380)71.7部、アクリル
[28,3部、ハイドロキノン0.1部、トリエチレン
ジアミン0.1部を還流器付、攪拌機付4つロフラスコ
に仕込み、空気を吹きこみながら90℃〜120°Cで
15〜20時間反応させ、酸価1以下とし、汲みだし、
樹脂(鶴とする。Production Example 5 71.7 parts of Epikote 828 (bisphenol type epoxy resin manufactured by Shell Chemical, molecule T380), 28.3 parts of acrylic, 0.1 part of hydroquinone, 0.1 part of triethylenediamine were prepared using a reflux device and 4 stirrers. Pour into a flask, let it react at 90°C to 120°C for 15 to 20 hours while blowing air, bring the acid value to below 1, and pump it out.
Resin (made into a crane).
製造例6
亜麻仁油脂肪酸20部、トリメチロールプロパン47部
を4つロフラスコ中N2ガス気流下で240℃で酸価5
以下まで反応させ、無水フタル酸33部を加え、同温度
で3時間反応させ、酸価5、OH価310の水酸基過剰
のアルキッドを得た。次にこのアルキッド71.5部、
シクロヘキサン10部、アクリル酸28.5部、P−エ
ンスルフォン&1.0部、ハイドロ−IP / ン0.
1部を環流器付4つロフラスコに仕込−+11空気を吹
き込みながら、90〜110℃で12時間反応させ、酸
価10の時点で、110〜120℃で2時間脱シクロヘ
キサンを行った。得られた樹脂は酸価8.2、粘度20
00ボイズ/25℃であった。Production Example 6 20 parts of linseed oil fatty acid and 47 parts of trimethylolpropane were heated to an acid value of 5 at 240°C under a stream of N2 gas in a flask.
33 parts of phthalic anhydride was added and the reaction was carried out for 3 hours at the same temperature to obtain an alkyd with an excess of hydroxyl groups and an acid value of 5 and an OH value of 310. Next, 71.5 parts of this alkyd,
10 parts of cyclohexane, 28.5 parts of acrylic acid, 1.0 part of P-ensulfone, 0.0 parts of Hydro-IP/N.
One part was placed in a four-hole flask equipped with a reflux device, and reacted at 90 to 110° C. for 12 hours while blowing −+11 air. When the acid value reached 10, cyclohexane was removed at 110 to 120° C. for 2 hours. The obtained resin had an acid value of 8.2 and a viscosity of 20.
00 voids/25°C.
実施例および比較例
表、1に示す組成物をそれぞれ、ブリキ板、TFS板、
アル°ミニウム板およびブリキ板にアルキッド樹脂、ビ
ニール樹脂もし、〈はアクリル樹脂の塗料を塗装し、た
各塗装板にRIテスターで3011F/ 100−の塗
布量で印刷し、カーテンビーム型電子線照射装置を用い
て10Mradの照射を行ない、硬化皮膜゛窄作製し、
た。The compositions shown in Table 1 of Examples and Comparative Examples were applied to tin plates, TFS plates,
If an aluminum plate or a tin plate is coated with alkyd resin or vinyl resin, then acrylic resin paint is applied to each coated plate, printed with an RI tester at a coating weight of 3011F/100-, and then irradiated with a curtain beam type electron beam. Irradiate at 10 Mrad using a device to create a cured film,
Ta.
その結果を表2に示す。The results are shown in Table 2.
表1に示すサンプル−1,3,5,7,9,11,につ
いて、ビニル系プライマーを塗装したブリキ板にRエテ
スターで30 mgr / 100 cdiの塗布量で
印刷し、その直後67 w / cmの@厩を有する2
kw高圧水銀灯の下10a++の断金コンベアに乗せ
、照射乾燥させた。Samples 1, 3, 5, 7, 9, and 11 shown in Table 1 were printed on a tin plate coated with a vinyl primer using an R tester at a coating amount of 30 mgr/100 cdi, and immediately after that, a coating amount of 67 w/cm was applied. 2 with @ stable
It was placed on a 10a++ cutting conveyor under a kW high-pressure mercury lamp and dried by irradiation.
得られた結果は表3に示す通りでおる。The results obtained are shown in Table 3.
表 3
(註) 硬化連直:指で強くこす9たIIK、ζすれ落
ちのない状態が得られる最高速度を示す〇
次に得られたサンプル−1,3,5,7,9,11のイ
ンキの印刷適性を調べるため、これらの各インキを用い
てハイデルKORI)単色印刷機でオフセット印刷した
。Table 3 (Note) Continuous hardening: 9 IIK rubbed strongly with fingers, ζ Indicates the maximum speed at which no slipping can be achieved 〇 Samples obtained next - 1, 3, 5, 7, 9, 11 In order to examine the printability of the inks, each of these inks was used for offset printing on a Heidel KORI (Heidel KORI) monochrome printing machine.
同時にインキlOグラムと水道水20グラムをホモミキ
サー3000回転で強制乳化し、過剰の水を取り除く。At the same time, 10 grams of ink and 20 grams of tap water were forcibly emulsified using a homomixer at 3000 rpm, and excess water was removed.
このようにして得られた乳化インキの水、乳化量の結果
は表4の逸りである。The results of the amount of water and emulsification of the emulsified ink thus obtained deviate from Table 4.
〔註〕 水乳化量:20−25−が最適で、2G−未満
では水余りし中すく、25嘔を超えると機上で乳化し中
すい。[Note] Amount of water emulsification: 20-25 is optimal; if it is less than 2G, there will be too much water and it will be empty, and if it exceeds 25g, it will be emulsified on the machine and it will be empty.
水中:数値は水あげ量で、例えば18〜26というのは
18未満では嘗ゴVが出て印刷出来ず、26を超えると
水が余って転移不良をおこす。Underwater: The numerical value is the amount of water added. For example, if the value is less than 18 and 18 to 26, smear V will come out and printing will not be possible, and if it exceeds 26, there will be excess water and poor transfer will occur.
Claims (1)
ポキシ化合物とラジカル重合性を有し、ないモノカルボ
ン酸との反応生成物 で示されるアクリル酸もしくはメタクリル酸エステル系
モノマー(aりり、、一般式(+)において、R1は水
素原子、メチル基、プロピル基もり、 <はブチル基を
、R2は水素原子もし、〈はメチル基を、nは1〜10
の整数を、Xはベンゼン環、アルキルベンゼン3[しく
はビスフェノール残基を、yは1〜4の整数を示す。) 印刷インキ組成物。 2 エポキシ化合物の分子量が200〜4000である
特許請求の範囲第1項記載の活性エネルギー線硬化性印
刷イシキ組成物。 3 エポキシ化合物が、ビスフェノールタイプエホキシ
化合物およびノボラックタイプエポキシ化合物から選ば
れる少なくとも1種である特許請求の範囲第1項または
第2項記載の活性エネルギー線硬化性印刷インキ組成物
。 4 エポキシ化合物とラジカル重合性を有しないモノカ
ルボン酸との反応生成物の軟化点が120℃以下である
特許請求の範囲第1項〜第3項いずれか記載の活性エネ
ルギー線硬化性印刷インキ組成物。[Scope of Claims] 1 (a) An acrylic acid or methacrylic acid ester monomer represented by a reaction product of an epoxy compound having one or more epoxy groups per molecule and a monocarboxylic acid that does not have radical polymerizability. In the general formula (+), R1 is a hydrogen atom, a methyl group, or a propyl group, < is a butyl group, R2 is a hydrogen atom, < is a methyl group, and n is 1 to 10
, X represents a benzene ring, alkylbenzene 3 or a bisphenol residue, and y represents an integer of 1 to 4. ) Printing ink composition. 2. The active energy ray-curable printing composition according to claim 1, wherein the epoxy compound has a molecular weight of 200 to 4,000. 3. The active energy ray-curable printing ink composition according to claim 1 or 2, wherein the epoxy compound is at least one selected from bisphenol type epoxy compounds and novolac type epoxy compounds. 4. The active energy ray-curable printing ink composition according to any one of claims 1 to 3, wherein the reaction product of an epoxy compound and a monocarboxylic acid that does not have radical polymerizability has a softening point of 120°C or less. thing.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57031787A JPS58149969A (en) | 1982-03-02 | 1982-03-02 | Energetic ray curing printing ink composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57031787A JPS58149969A (en) | 1982-03-02 | 1982-03-02 | Energetic ray curing printing ink composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58149969A true JPS58149969A (en) | 1983-09-06 |
JPS6412312B2 JPS6412312B2 (en) | 1989-02-28 |
Family
ID=12340765
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57031787A Granted JPS58149969A (en) | 1982-03-02 | 1982-03-02 | Energetic ray curing printing ink composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58149969A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01168769A (en) * | 1987-12-24 | 1989-07-04 | Toyo Ink Mfg Co Ltd | Covering composition curable by actinic radiation |
-
1982
- 1982-03-02 JP JP57031787A patent/JPS58149969A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01168769A (en) * | 1987-12-24 | 1989-07-04 | Toyo Ink Mfg Co Ltd | Covering composition curable by actinic radiation |
Also Published As
Publication number | Publication date |
---|---|
JPS6412312B2 (en) | 1989-02-28 |
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