JPH0246460A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPH0246460A JPH0246460A JP19733688A JP19733688A JPH0246460A JP H0246460 A JPH0246460 A JP H0246460A JP 19733688 A JP19733688 A JP 19733688A JP 19733688 A JP19733688 A JP 19733688A JP H0246460 A JPH0246460 A JP H0246460A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polyether urethane
- hydrophilic
- composition
- water
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- 239000000203 mixture Substances 0.000 abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 abstract description 6
- 229920005862 polyol Polymers 0.000 abstract description 6
- 150000003077 polyols Chemical class 0.000 abstract description 6
- 239000005056 polyisocyanate Substances 0.000 abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- -1 polyoxyethylene Polymers 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000000976 ink Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VTRHYFDNOLMPHD-UHFFFAOYSA-N (1-prop-2-enoyloxycyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(OC(=O)C=C)CCCCC1 VTRHYFDNOLMPHD-UHFFFAOYSA-N 0.000 description 1
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-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
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- BVEYJWQCMOVMAR-UHFFFAOYSA-N 5-Hydroxy-4-octanone Chemical compound CCCC(O)C(=O)CCC BVEYJWQCMOVMAR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960002130 benzoin Drugs 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- MHLHYHIKXDADCI-UHFFFAOYSA-L disodium;2-phosphonatoethanol Chemical compound [Na+].[Na+].OCCP([O-])([O-])=O MHLHYHIKXDADCI-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 238000000034 method Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- ILDHRKXCSXNADL-UHFFFAOYSA-M sodium;bis(hydroxymethyl)phosphinate Chemical compound [Na+].OCP([O-])(=O)CO ILDHRKXCSXNADL-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DSROZUMNVRXZNO-UHFFFAOYSA-K tris[(1-naphthalen-1-yl-3-phenylnaphthalen-2-yl)oxy]alumane Chemical compound C=1C=CC=CC=1C=1C=C2C=CC=CC2=C(C=2C3=CC=CC=C3C=CC=2)C=1O[Al](OC=1C(=C2C=CC=CC2=CC=1C=1C=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)OC(C(=C1C=CC=CC1=C1)C=2C3=CC=CC=C3C=CC=2)=C1C1=CC=CC=C1 DSROZUMNVRXZNO-UHFFFAOYSA-K 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、水、アルカリ水、あるいは界面活性剤等を含
有する水系による現像が可能である感光性樹脂服用組成
物に関し、特に水系現像が可能である感光性フレキソ版
材用の組成物に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin composition that can be developed with water, alkaline water, or an aqueous system containing a surfactant. The present invention relates to a composition for a photosensitive flexo plate material that is possible.
（従来の技術）
従来より感光性樹脂版には、現像液として有機溶剤を用
いるタイプと水、アルカリ水、界面活性剤等を含有した
水系現像タイプが知られている。(Prior Art) Conventionally, photosensitive resin plates have been known to include a type that uses an organic solvent as a developer and an aqueous development type that contains water, alkaline water, a surfactant, and the like.
しかしながら従来技術のうち有機溶剤現像タイプの場合
、公害対策、作業環境、防火等の点で現像装置の完全密
閉化、空調設備の完備、防爆装置の設置等の処置を講じ
なければいけないという欠点があった。However, among conventional technologies, the organic solvent development type has the disadvantage that measures such as completely sealing the developing device, providing air conditioning equipment, and installing explosion-proof equipment are required in terms of pollution control, work environment, fire prevention, etc. there were.
一方、水現像タイプの場合でも、組成物の親水性が高い
ため光重合後、組成物の耐水性が劣るという欠点があっ
た。On the other hand, even in the case of the water-developable type, there was a drawback that the water resistance of the composition after photopolymerization was poor due to the high hydrophilicity of the composition.
また、水系現像フレキソ版に関しては、例えば特開昭５
４−１１０２８７号、特開昭５８−１１７５３７号など
が知られている。しかしながら前者は現像液がいずれも
例えば水酸化ナトリウム／イソプロピルアルコール／水
、炭酸ナトリウム／２−ブトキシェタノール／水、硫酸
ナトリウム／２−ブトキシェタノール／水等のアルコー
ル／アルカリ水系であって、水を単独に現像液として使
用するものではなかった。また後者は、主成分となるポ
リマーがカチオン系ポリエステルアミドであり耐加水分
解性に問題が残るという欠点があった。Regarding aqueous development flexo plates, for example,
No. 4-110287, JP-A-58-117537, etc. are known. However, in the former case, the developer is an alcohol/alkaline aqueous system such as sodium hydroxide/isopropyl alcohol/water, sodium carbonate/2-butoxycetanol/water, sodium sulfate/2-butoxycetanol/water, etc. was not intended to be used alone as a developer. Furthermore, the latter had the disadvantage that the main component polymer was a cationic polyester amide and there remained a problem in hydrolysis resistance.
その他ポリエーテル鎖をソフトセグメントとするポリマ
ーを用いたフレギソ版組成物に関しては、例えば特開昭
５０−７６０３号、特開昭５０−６４０３号、特開昭５
１−１７２８５号、特開昭４９−１０９１０４号、特開
昭４９３２７０２号、特開昭４９−３３７０２号、特開
昭４９−１１０４０２号、及び特開昭５９４１３４３０
号等が知られている。Regarding other Fregiso plate compositions using polymers having polyether chains as soft segments, for example, JP-A-50-7603, JP-A-50-6403, JP-A-5
1-17285, JP 49-109104, JP 4932702, JP 49-33702, JP 49-110402, and JP 59413430
The number etc. are known.
しかしながらこれはいずれも液状タイプであり、固体状
の水系現像型のものは報告されていない。However, all of these are liquid types, and solid water-based developable ones have not been reported.
（発明が解決しようとする課題）
本発明は、水系現像が可能である感光性樹脂板における
前記従来の欠点、即ち光重合物の耐水性の限界、アルコ
ール含有水系現像液の使用、及び光重合前が液状タイプ
等の点を解消し、水単独で現像でき、固形板であり光重
今後十分な耐水性を有しかつ水系フレキソインキに対し
て十分なインキ転移性を有する感光性樹脂板組成物を提
供せんとするものである。(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks of the conventional photosensitive resin plates that can be developed in water, namely, the limited water resistance of photopolymerized materials, the use of alcohol-containing water-based developers, and the problem of photopolymerization. A photosensitive resin plate composition that eliminates the problems of the liquid type, can be developed with water alone, is a solid plate, has sufficient water resistance for light weight, and has sufficient ink transferability for water-based flexographic inks. It is intended to provide something.
（課題を解決するための手段）
（Ｂ）エチレン性不飽和化合物 ３〜５０重量％（Ｃ
）光重合開始剤 ０．１〜２重量％を含有すること
を特徴とする感光性樹脂組成物である。(Means for solving the problem) (B) Ethylenically unsaturated compound 3-50% by weight (C
) A photosensitive resin composition characterized by containing 0.1 to 2% by weight of a photopolymerization initiator.
本発明において（Ａ）成分は親水性ポリエーテルウレタ
ンと疎水性ポリマーとがＩ：９９〜９９：１、好ましく
は１０ ： ９０〜９０ ： １０の割合（重量比）で
混合されたものであり、この中の親水性ポリエーテルウ
レタンを構成するポリエーテル成分としては、例えば数
平均分子量が２００〜１０．０００であるポリオキシエ
チレンポリオール、ポリオキシプロピレンポリオール及
びポリオキシテトラメチレンポリオール等のポリオキシ
アルキレンポリオールを挙げることが出来る。In the present invention, component (A) is a mixture of hydrophilic polyether urethane and hydrophobic polymer at a ratio (weight ratio) of I:99 to 99:1, preferably 10:90 to 90:10, Examples of the polyether component constituting the hydrophilic polyether urethane include polyoxyalkylene polyols such as polyoxyethylene polyols, polyoxypropylene polyols, and polyoxytetramethylene polyols having a number average molecular weight of 200 to 10,000. can be mentioned.
ポリエーテルウレタンを構成する場合の他の必須成分で
あるポリイソシアナ−１・とじては各種のものが例示さ
れる。例えばジフェニルメタンジイソシアナート（ＭＤ
Ｉ） 、ｌ−リレンジイソシアナー） （ＴＤＩ）、キ
シリレンジイソシアナート（ＸＤＩ ）、ヘキザメチレ
ンジイソシアナーｌ−（＋１１１１）等のジイソシアナ
−１・、トリフェニルメタントリイソシアナート、ポリ
メチレンポリフェニルイソシアナト等のポリイソシアナ
ートを挙げることが出来る。Various polyisocyanates are exemplified as polyisocyanate-1, which is another essential component when constituting polyether urethane. For example, diphenylmethane diisocyanate (MD
I), diisocyana-1, such as l-lylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate l-(+1111), triphenylmethane triisocyanate, polymethylene poly Mention may be made of polyisocyanates such as phenyl isocyanate.
また（八）成分である親水性基を有するポリエテルウレ
タンとは親水性基を主鎖または側鎖に含むポリエーテル
ウレタンであり、その親水性基としてポリエチレングリ
コール基、ヒドロキシル基等のノニオン性基、カルボキ
シル基、スルホン酸基、リン酸基、ホスフィン酸基、ホ
スフィン酸基等のアニオン性基、及び第３級窒素原子を
含むアミノ基、第４級アンモニウム基等のカチオン性基
等が挙げられる。これら親水性基をポリマーの主鎖又は
側鎖中に単独もしくは併用して導入することでそのポリ
マーを水又はアルカリ水溶液に対して著しく膨潤させる
ことができる。これらの親水性基を導入する具体的な方
法として、上述した親水性基と同一分子内にイソシアナ
ート基で反応し得る活性水素原子を２個含有する化合物
、例えばポリエチレングリコール、ジメチロールプロピ
オン酸、ジアミノヘンセンスルホン酸ナトリウム、グリ
セリン千ノリン酸エステル２ナトリウム塩、ヒドロキシ
エチル、ヒドロキシエチルホスフォン酸ナトリウム、ジ
メチロールホスフィン酸ナトリウム、Ｎメチルエタノー
ルアミン、及びＮ、Ｎジメチルジェタノールアンモニウ
ムクロライド等をポリマー原料として共重合して容易に
人手することができる。これらの親水性基を導入して得
られる親水性ポリエーテルウレタンとは、２０°Ｃの水
、又はクアルカリ水溶液中に２４時間浸漬した場合溶解
又は分散するか、もしくは少なくともポリマーの重量増
加率が２００％以上であるような親水性を有するポリマ
ーである。In addition, the component (8) polyether urethane having a hydrophilic group is a polyether urethane containing a hydrophilic group in the main chain or side chain, and the hydrophilic group is a nonionic group such as a polyethylene glycol group or a hydroxyl group. , carboxyl groups, sulfonic acid groups, phosphoric acid groups, phosphinic acid groups, anionic groups such as phosphinic acid groups, and cationic groups such as amino groups containing tertiary nitrogen atoms, quaternary ammonium groups, etc. . By introducing these hydrophilic groups into the main chain or side chain of a polymer, either singly or in combination, the polymer can be significantly swollen in water or an aqueous alkaline solution. A specific method for introducing these hydrophilic groups is to use a compound containing two active hydrogen atoms capable of reacting with an isocyanate group in the same molecule as the above-mentioned hydrophilic group, such as polyethylene glycol, dimethylolpropionic acid, Polymer raw materials include sodium diaminohense sulfonate, glycerin thinophosphate disodium salt, hydroxyethyl, sodium hydroxyethylphosphonate, sodium dimethylolphosphinate, N-methylethanolamine, and N,N-dimethyljetanol ammonium chloride. It can be easily copolymerized by hand. The hydrophilic polyether urethane obtained by introducing these hydrophilic groups is one that dissolves or disperses when immersed in water at 20°C or aqueous alkaline solution for 24 hours, or has a polymer weight increase rate of at least 200°C. % or more.
本発明において疎水性ポリマーとは、疎水性ポリエーテ
ルウレタンに限らず上記に示したような２０°Ｃの水又
はアルカリ水溶液中に２４時間浸漬した時にその重量増
加率が１００％以下であるようなポリマーであり、かつ
上記した親水性ポリエーテルウレタンと相溶性が良好な
ポリマーである。In the present invention, hydrophobic polymers are not limited to hydrophobic polyether urethane, but include those whose weight increase rate is 100% or less when immersed in water or alkaline aqueous solution at 20°C for 24 hours as shown above. It is a polymer and has good compatibility with the above-mentioned hydrophilic polyether urethane.
なお、本発明における親水性あるいは疎水性ポリエーテ
ルウレタンは前記成分の他に必要に応じて種々のグリコ
ール成分によって鎖延長することが出来る。具体的には
、例えばエチレングリコール、プロピレングリコール、
ネオペンチルグリコール、ヘキサメチレングリコール等
の炭素数１〜６の脂肪族ジオールジエチレングリコール
、ジプロピレレグリコール等のエーテルグリコール類。The hydrophilic or hydrophobic polyether urethane in the present invention can be chain-extended with various glycol components in addition to the above-mentioned components, if necessary. Specifically, for example, ethylene glycol, propylene glycol,
C1-6 aliphatic diols such as neopentyl glycol and hexamethylene glycol; ether glycols such as diethylene glycol and dipropylene glycol;
等で示される芳香族ジオール、エチレンジアミン、１．
６−ヘキサメチレンジアミン、イソホロンジアミン等の
脂肪族ジアミン、数平均分子量がｌＯＯ〜１０，０００
の範囲にあるポリエチレングリコールジアミン、ポリプ
ロピレングリコールジアミン等のポリエーテルポリアミ
ンあるいは、数平均分子量が５００〜１０，０００の範
囲にあるブタジェン系ジアミン等を挙げることができる
。Aromatic diols such as ethylenediamine, 1.
Aliphatic diamines such as 6-hexamethylene diamine and isophorone diamine, with a number average molecular weight of 100 to 10,000
Examples include polyether polyamines such as polyethylene glycol diamine and polypropylene glycol diamine having a number average molecular weight in the range of 500 to 10,000, and butadiene diamines having a number average molecular weight in the range of 500 to 10,000.
本発明における前記のポリエーテルウレタンは通常の方
法により製造することが出来る。即ちポリエーテルグリ
コール及びポリイソシアネートよりプレポリマーを合成
し、その後、各種成分あるいはジアミン成分により鎖延
長し、溶剤を除去することにより得ることが出来る。The polyether urethane in the present invention can be produced by a conventional method. That is, it can be obtained by synthesizing a prepolymer from polyether glycol and polyisocyanate, then chain-extending it with various components or diamine components, and removing the solvent.
次に本発明における（Ｂ）成分であるエチレン性不飽和
化合物は、少なくとも１個の末端エチレン性基を含有す
る化合物であり、この化合物は遊離ラジカルにより開始
された連鎖生長付加重合により高分子重合体を形成し得
るものである。適当なエチレン性不飽和化合物はポリオ
ール類の不飽和エステル特にアルファメチレンカルボン
酸類とのかかるエステル類、例えば、エチレングリコー
ルジアクリレート、グリセロールジアクリレート、エチ
レングリコールジメタアクリレート、１．３プロパンジ
オールジメタアクリレート、１，２゜４−ブタントリオ
ールトリアクリレート、１．４シクロヘキサンジオール
ジアクリレート、１゜３−プロパンジオールジアクリレ
ート、１． ６ヘキサンジオールジアクリレート、トリ
メチロールプロパントリアクリレート等が挙げられる。Next, the ethylenically unsaturated compound which is component (B) in the present invention is a compound containing at least one terminal ethylenic group, and this compound is polymerized by chain propagation addition polymerization initiated by free radicals. It is possible to form a union. Suitable ethylenically unsaturated compounds are unsaturated esters of polyols, especially such esters with alpha methylene carboxylic acids, such as ethylene glycol diacrylate, glycerol diacrylate, ethylene glycol dimethacrylate, 1.3 propanediol dimethacrylate. , 1,2゜4-butanetriol triacrylate, 1.4 cyclohexanediol diacrylate, 1゜3-propanediol diacrylate, 1. Examples include 6-hexanediol diacrylate and trimethylolpropane triacrylate.
本発明における（Ｂ）成分の組成物中の含有量は、３〜
５０重量％の範囲であるのが好ましく、特に１０〜４０
重量％の範囲であるのが好ましい。含有量が３重量％未
満の場合には架橋密度が著しく低下し光重合物が十分な
耐水性を示さずさらには現像時満足な画線を得ることが
出来ないという欠点を生じる。又、逆に５０重量％を越
える場合には、架橋密度が高くなり、版組成物の硬度が
高くなって、フレキソ印刷版として要求されるゴム弾性
を発現しなくなるので好ましくない。In the present invention, the content of component (B) in the composition is 3 to 3.
It is preferably in the range of 50% by weight, especially from 10 to 40% by weight.
A range of % by weight is preferred. If the content is less than 3% by weight, the crosslinking density will drop significantly, resulting in the disadvantage that the photopolymerized product will not exhibit sufficient water resistance and, furthermore, it will not be possible to obtain satisfactory images during development. On the other hand, if it exceeds 50% by weight, the crosslinking density becomes high, the hardness of the plate composition becomes high, and the rubber elasticity required for a flexographic printing plate is not exhibited, which is not preferable.
次に本発明において（Ｃ）成分である光重合開始溶剤と
は、活性光線により活性種を発生し、光ラジカル重合を
開始し得るものである。有用な光重合開始剤、は公知の
各種化合物を使用することができ、具体的には隣接ポリ
ケトン化合物、例えばジアセチル、ベンジルその他、α
−カルボニルアルコール例えばベンゾイン、ブチロイン
その他、アシロインエーテル、例えば、ベンゾインメチ
ルエーテル、ベンゾインエチルエーテル、α−置換アシ
ロイン、例えばα−アルキルベンゾインα−アルコキシ
アシロインその他、及び多核キノンその他等が挙げられ
、これらを単独または併用して使用される。光重合開始
剤は組成物中に０．１〜２重量％、好ましくは０．５〜
１重量％の範囲で含有することが出来る。Next, in the present invention, the photopolymerization initiating solvent, component (C), is one that can generate active species by actinic rays and initiate photoradical polymerization. Various known compounds can be used as useful photopolymerization initiators, and specifically, vicinal polyketone compounds such as diacetyl, benzyl, etc.
-Carbonyl alcohols such as benzoin, butyroin, etc., acyloin ethers, such as benzoin methyl ether, benzoin ethyl ether, α-substituted acyloins, such as α-alkylbenzoin, α-alkoxyacyloin, etc., and polynuclear quinones, etc.; used alone or in combination. The photopolymerization initiator is contained in the composition in an amount of 0.1 to 2% by weight, preferably 0.5 to 2% by weight.
It can be contained in a range of 1% by weight.
なお本発明において、前記成分以外にさらに光架橋反応
を抑制することなく単に熱重合のみを防止するために熱
重合禁止剤を組成物中に０〜１重量％、好ましくは０．
２〜０．７重量％の範囲で含有させてもよい。有用な熱
重合禁止剤としては、例えば、ハイドロキノン、ハイド
ロキノンモノメチルエーテル、カテコール、ｐ−ｔ−ブ
チルカテコール等が挙げられる。In addition, in the present invention, in addition to the above-mentioned components, a thermal polymerization inhibitor is added to the composition in an amount of 0 to 1% by weight, preferably 0.5% by weight, in order to simply prevent thermal polymerization without further suppressing the photocrosslinking reaction.
It may be contained in a range of 2 to 0.7% by weight. Useful thermal polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, and the like.
（作 用）
本発明組成物が水現像性とレリーフの耐水性の両立とい
う二律背反した性能を示す理由としては明らかではない
が、親水性ポリマーが連続相を、疎水性ポリマーが分散
相を形成し、その界面において適度に相溶化が生ずるた
めと類推される。(Function) Although it is not clear why the composition of the present invention exhibits the contradictory performance of achieving both water developability and relief water resistance, the hydrophilic polymer forms a continuous phase and the hydrophobic polymer forms a dispersed phase. , it is assumed that this is due to moderate compatibilization occurring at the interface.
（実施例）
以下本発明を実施例により具体的に説明するが本発明は
これに限定されるものではない。(Examples) The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.
合成例１
撹拌装置付き反応器に分子量１．１００のポリテトラメ
チレングリコール＋−５０、０ｇ、にヘキサメチレンジ
イソシアナート９７．３ ｇを加えＮ２雰囲気下１１０
°Ｃで６時間反応させプレポリマーを得た。更にヘキサ
メチレングリコール６０．０ ｇ、ジ−ｎ−ブチルＳｎ
ジラウレート０．９ｇをジメチルアセトアミド４５０ｇ
に溶解し、その溶液を前記のプレポリマーに加えＮ２雰
囲気下８０°Ｃで４時間反応させ、残存イソシアナート
のＩＲ吸収スペクトル（２２１５ｃｍ−’）が消失する
ことを確認することにより反応を終了した。ジメチルア
セトアミドを減圧除去することによりゴム弾性を有する
疎水性ポリエーテルウレタンを得た。Synthesis Example 1 97.3 g of hexamethylene diisocyanate was added to polytetramethylene glycol +-50.0 g with a molecular weight of 1.100 in a reactor equipped with a stirring device, and the mixture was heated to 110 g under an N2 atmosphere.
A prepolymer was obtained by reacting at °C for 6 hours. Furthermore, 60.0 g of hexamethylene glycol, di-n-butyl Sn
Dilaurate 0.9g to dimethylacetamide 450g
The solution was added to the above prepolymer and reacted for 4 hours at 80°C under N2 atmosphere, and the reaction was terminated by confirming that the IR absorption spectrum (2215 cm-') of the remaining isocyanate disappeared. . Hydrophobic polyether urethane having rubber elasticity was obtained by removing dimethylacetamide under reduced pressure.
（以下ポリマーＡという）。(hereinafter referred to as Polymer A).
合成例２
分子量１，１００のポリテトラメチレングリコール１５
０．０ｇへキザメチレンジイソシアナート（＋１０１）
４３．２ｇを撹拌装置付き反応器に加え合成例と同様に
してプレポリマーを得た。ジメチロールプロピオン酸２
０ｇ１ジーｎ−ブチルＳｎジラウレート０．９ｇをジメ
チルアセトアミド４５０ｇに溶解し、ｔｉｉｌ記のプレ
ポリマーに加えＮ２雰囲気下８０°Ｃで４時間反応させ
た。残存イソシアナートのＩｌ？吸収スペクＩ・ル（２
２１５ｃｎｒ’）が消失することを確認することにより
反応を終了した。ジメチルアセトアミドを減圧除去しゴ
ム弾性を有する親水性ポリエーテルウレタンを得た（以
下ポリマーＢという）。Synthesis Example 2 Polytetramethylene glycol 15 with a molecular weight of 1,100
0.0g Quizamethylene diisocyanate (+101)
43.2 g was added to a reactor equipped with a stirring device to obtain a prepolymer in the same manner as in the synthesis example. dimethylolpropionic acid 2
0.9 g of di-n-butyl Sn dilaurate was dissolved in 450 g of dimethylacetamide, and the solution was added to the prepolymer described in section 3 and reacted at 80° C. for 4 hours under N2 atmosphere. Il of residual isocyanate? Absorption Spec I Le (2
The reaction was terminated by confirming that 215cnr') had disappeared. Dimethylacetamide was removed under reduced pressure to obtain a hydrophilic polyether urethane having rubber elasticity (hereinafter referred to as Polymer B).
合成例３
合成例２において、ｌＩＤ１４６．５ｇ、ジメチロール
プロピオン酸２３．０ｇとする以外は、合成例２と同様
の操作によりゴム弾性を有する親水性ポリエーテルウレ
タンを得た（以下ポリマーＣという）。Synthesis Example 3 A hydrophilic polyether urethane having rubber elasticity was obtained in the same manner as in Synthesis Example 2, except that 146.5 g of lID and 23.0 g of dimethylolpropionic acid were used in Synthesis Example 2 (hereinafter referred to as Polymer C). .
合成例４
分子ｆｆ１ｌ、＋００のポリテ１−ラメチレングリ：１
−ル１５０ｇ、 Ｈｌ）１４１．４ｇを合成例１と同様
にして反応させプレポリマーを得た。リチウム塩化した
ビスヒドロキシエチルアミノエタンスルホン酸２７．０
ｇ及びジ−ｎ−ブチルＳｎジラウレート０．９ｇをジ
メチルアセトアミド４５０ｇに溶解し、前記したプレポ
リマに加えＮ２雰囲気下８０°Ｃで４時間反応させ、残
存イソシアナート基のＩＲ吸収スペクトル（Ｖ−２２１
５ｃｍ−’）が消失することを確認することにより反応
を終了した。ジメチルアセトアミドを減圧除去すること
によりゴム弾性を有する親水性ポリエーテルウレタンを
得た（以下ポリマーＤという）。Synthesis Example 4 Molecule ff1l, +00 polyte 1-ramethylene glycol: 1
150 g of H1 and 141.4 g of H1 were reacted in the same manner as in Synthesis Example 1 to obtain a prepolymer. Lithium chloride bishydroxyethylaminoethanesulfonic acid 27.0
g and di-n-butyl Sn dilaurate (0.9 g) were dissolved in 450 g of dimethylacetamide, added to the above-mentioned prepolymer, and reacted at 80°C for 4 hours under N2 atmosphere to obtain an IR absorption spectrum (V-221
The reaction was terminated by confirming that 5 cm-') had disappeared. By removing dimethylacetamide under reduced pressure, a hydrophilic polyether urethane having rubber elasticity was obtained (hereinafter referred to as Polymer D).
合成例５
合成例４においてＨＤＩ ５１．０ ｇリチウム塩化
したビスヒドロキシエチルエタンスルホン酸４０．０
ｇとする以外は合成例４と同様にして親水性ポリエーテ
ルウレタンを得た（以下ポリマーＥという）。Synthesis Example 5 In Synthesis Example 4, HDI 51.0 g lithium chlorinated bishydroxyethylethanesulfonic acid 40.0
A hydrophilic polyether urethane was obtained in the same manner as in Synthesis Example 4, except for using G (hereinafter referred to as Polymer E).
合成例６
合成例４においてＨＤＩ ８１．４ｇリチウム塩化し
たビスヒドロキシエチルエタンスルホン酸８０．０ｇと
した以外は合成例４と同様にして親水性ポリエーテルウ
レタンを得た（以下ポリマーＦという）。Synthesis Example 6 A hydrophilic polyether urethane was obtained in the same manner as in Synthesis Example 4 except that 81.4 g of HDI and 80.0 g of lithium-chlorinated bishydroxyethylethanesulfonic acid were used (hereinafter referred to as Polymer F).
合成例７
合成例４において１１０１ ２２．５ｇリチウム塩化し
たビスヒドロキシエチルエタンスルホン酸２．５ｇとす
る以外は合成例４と同様の操作により疎水性ポリエーテ
ルウレタンを得た（以下ポリマーＧという）。Synthesis Example 7 A hydrophobic polyether urethane (hereinafter referred to as Polymer G) was obtained in the same manner as in Synthesis Example 4 except that 22.5 g of 1101 and 2.5 g of lithium-chlorinated bishydroxyethylethanesulfonic acid were used.
合成例８
分子量８５０のポリテトラメチレングリコール７．６ｇ
、、ｌＩＤ１２１．８ｇジメチロールプロピオン酸１
５．４ ｇ及びジｎ−ブチルＳｎジラウレート１．０ｇ
をヒＩ−ラヒド口フラン３００ｇに溶解した溶液を撹拌
機のついた１１フラスコにいれ６５°Ｃで３時間反応を
続けた。別の容器で、末端アミン基含有アクリロニトリ
ル・ブタジェンオリゴマー（Ｉｌｙｃａｖ ＡＴＢＮ
１３００ Ｘ １６宇部興産■製）５５．３ｇをテトラ
ヒドロフラン１００ｇに溶解して調製した溶液を上記の
１！フラスコ内に室温下で撹拌しながら添加した。得ら
れたポリマ−溶液、水酸化リチウム４．８ｇをメチルア
ルコール１００ｇに溶解した溶液を室温下で撹拌しなが
ら添加しさらに３０分間撹拌することによって親水性ポ
リエーテルウレタンを得た（以下ポリマー１１という）
。Synthesis Example 8 7.6 g of polytetramethylene glycol with a molecular weight of 850
,, ID121.8g dimethylolpropionic acid 1
5.4 g and di-n-butyl Sn dilaurate 1.0 g
A solution prepared by dissolving 300 g of Hydrahydrofuran was placed in a flask equipped with a stirrer, and the reaction was continued at 65°C for 3 hours. In a separate container, acrylonitrile butadiene oligomer containing terminal amine groups (Ilycav ATBN
A solution prepared by dissolving 55.3 g of 1300 x 16 (manufactured by Ube Industries, Ltd.) in 100 g of tetrahydrofuran was prepared as described in step 1 above. It was added into the flask at room temperature while stirring. A solution of 4.8 g of lithium hydroxide dissolved in 100 g of methyl alcohol was added to the obtained polymer solution while stirring at room temperature, and the mixture was further stirred for 30 minutes to obtain a hydrophilic polyether urethane (hereinafter referred to as Polymer 11). )
.
合成例１〜８で得られた各親水性及び疎水性ポリエーテ
ルの親水基含有量を表１に示す。Table 1 shows the hydrophilic group content of each hydrophilic and hydrophobic polyether obtained in Synthesis Examples 1 to 8.
実施例１
ポリマーＡ Ｉ７．５ ｇポリマー８５２．５ ｇへキ
サメチレングリコールジアクリレ−１２８，５、ベンジ
ルジメチルケクール１ｇ及びハイドロキノンモノメチル
エーテル０．５ｇ加熱ニーダ−を用いて１０５°Ｃで混
練し、脱泡後、得られた感光性樹脂組成物をヒートプレ
ス機で１０５°Ｃ、１００ｋｇ ／ ａｆｔの圧力で、
１２５ μ＋ｎ厚みのポリエステルフィルムと、同じポ
リエステルフィルム上に２μｍのポリビニールアルコー
ルを片面にコートしたポリエステルフィルム間で、ポリ
ビニルアルコールコート層が感光性樹脂と接するよう１
分間加熱加圧して厚さ２．８画のシートを作成した。Example 1 Polymer A I7.5 g Polymer 852.5 g Hexamethylene glycol diacrylate-128.5, Benzyl dimethyl kecool 1 g and hydroquinone monomethyl ether 0.5 g Kneaded at 105°C using a heating kneader After defoaming, the resulting photosensitive resin composition was heated in a heat press at 105°C and a pressure of 100 kg/aft.
Between a polyester film with a thickness of 125 µ+n and a polyester film coated with 2 µm of polyvinyl alcohol on one side on the same polyester film, 1
A sheet having a thickness of 2.8 strokes was prepared by heating and pressing for minutes.
最上層のポリエステルフィルムを剥離して感光性樹脂層
上にポリビニルアルコール膜を残し、画像を有するネガ
フィルムをその上に密着して水銀灯（大日本スクリーン
社製）で、照度２５Ｗ／ｎｆ根、５分間露光を行った。The top layer of polyester film was peeled off to leave a polyvinyl alcohol film on the photosensitive resin layer, and a negative film with an image was adhered thereon and exposed to a mercury lamp (manufactured by Dainippon Screen Co., Ltd.) at an illuminance of 25 W/nf, 5 Exposure was performed for minutes.
ネガフィルムを除いた後、アルキルナフタレンスルホン
酸ソーダ２重量％を含有する中性水で４０°Ｃ１５分間
、ブラシによる現像を行ったところ、レリーフの深度１
、２ ｍｍの画像パターンが得られた。この画像パタ
ーンは使用したネガフィルムの画像を忠実に再現してい
た。また得られたレリーフは、インキの受理転移性もよ
く、鮮明な画像を示していた。After removing the negative film, development was performed with a brush at 40°C for 15 minutes in neutral water containing 2% by weight of sodium alkylnaphthalene sulfonate, and the relief depth was 1.
, 2 mm image patterns were obtained. This image pattern faithfully reproduced the image of the negative film used. Furthermore, the obtained relief had good ink acceptance and transferability and showed a clear image.
実施例２
実施例１においてポリマーＡ３５ｇ、ポリマーＢ５５ｇ
とした以外全て実施例１と同様にしてレリーフパターン
を得たところがフィルムの画像を忠実に再現し、インキ
の受理転移性、耐溶剤性が優れたレリーフが得られた。Example 2 In Example 1, 35 g of polymer A, 55 g of polymer B
A relief pattern was obtained in the same manner as in Example 1 except for the following, and a relief that faithfully reproduced the image on the film and had excellent ink transferability and solvent resistance was obtained.
実施例３
実施例１においてポリマーＡ１７．５ｇ、ポリマーＣ５
２，５ｇとした以外全て実施例１と同様にしてしリーフ
パターンを得たところネガフィルムの画像を忠実に再現
し、インキの受理転移性、耐溶剤性が優れたレリーフが
得られた。Example 3 In Example 1, 17.5 g of polymer A, 5 g of polymer
A relief pattern was obtained in the same manner as in Example 1 except that the amount was 2.5 g, and the relief faithfully reproduced the image of the negative film and had excellent ink transferability and solvent resistance.
実施例４
実施例１においてポリマーＡ３５．０ｇ、ポリマーＣ３
５，Ｏｇとした以外全て実施例１と同様にしてレリーフ
パターンを得たところネガフィルムの画像を忠実に再現
し、インキの受理転移性、耐溶剤性が優れたレリーフが
得られた。Example 4 In Example 1, 35.0 g of polymer A, 3 polymer C3
A relief pattern was obtained in the same manner as in Example 1 except that 5.0g was used, and a relief was obtained that faithfully reproduced the image of the negative film and had excellent ink acceptance transferability and solvent resistance.
実施例５
実施例１においてポリマーＡ３５．０ｇ、ポリマーＦ
３５．０ ｇとした以外全て実施例１と同様にしてレリ
ーフパターンを得たところネガフィルムの画像を忠実に
再現し、インキの受理転移性、耐溶剤性が優れたレリー
フが得られた。Example 5 In Example 1, 35.0 g of Polymer A, Polymer F
A relief pattern was obtained in the same manner as in Example 1 except that the weight was changed to 35.0 g. A relief pattern was obtained that faithfully reproduced the image of the negative film and had excellent ink acceptance transferability and solvent resistance.
実施例６
実施例１においてポリマーＤ ３５．０ ｇ、ポリマー
Ｇ３５．Ｏｇとした以外全て実施例１と同様にしてレリ
ーフパターンを得たところネガフィルムの画像を忠実に
再現し、インキの受理転移性、耐溶剤性が優れたレリー
フが得られた。Example 6 In Example 1, 35.0 g of Polymer D, 35.0 g of Polymer G. A relief pattern was obtained in the same manner as in Example 1 except that Og was used, and a relief that faithfully reproduced the image of the negative film and had excellent ink transferability and solvent resistance was obtained.
実施例７
実施例１においてポリマーＥ３５．０ｇ、ポリマーＧ
３５．Ｏｇとした以外全て実施例１と同様にしてレリー
フパターンを得たところネガフィルムの画像を忠実に再
現し、インキの受理転移性、耐溶剤性が優れたレリーフ
が得られた。Example 7 In Example 1, 35.0 g of polymer E, polymer G
35. A relief pattern was obtained in the same manner as in Example 1 except that Og was used, and a relief that faithfully reproduced the image of the negative film and had excellent ink transferability and solvent resistance was obtained.
実施例８
実施例１においてポリマーＨ３５，Ｏｇ、ポリエピクロ
ルヒドリン（エビクロマ−Ｈ大阪曹達■製）３５．０ｇ
とした以外全て実施例１と同様にしてレリーフパターン
を得たところネガフィルムの画像を忠実に再現し、イン
キの受理転移性、耐溶剤性が優れたレリーフが得られた
。Example 8 In Example 1, polymer H35, Og, polyepichlorohydrin (Ebichroma-H Osaka Soda ■) 35.0 g
A relief pattern was obtained in the same manner as in Example 1 except for the following steps. A relief pattern was obtained that faithfully reproduced the image of the negative film and had excellent ink acceptance and transfer properties and solvent resistance.
実施例９
実施例１においてポリマーＨ３５，Ｏｇ、塩素化ポリエ
チレン（Ｈ１３５大阪曹達■製） ３５．０ ｇとした
以外全て実施例１と同様にしてレリーフパターンを得た
ところネガフィルムの画像を忠実に再現し、インキの受
理転移性、耐溶剤性が優れたレリーフが得られた。Example 9 A relief pattern was obtained in the same manner as in Example 1 except that the polymer H35, Og and chlorinated polyethylene (H135 manufactured by Osaka Soda ■) were changed to 35.0 g, and the image on the negative film was faithfully reproduced. Reliefs with excellent ink transferability and solvent resistance were obtained.
比較例工〜牛
合成例で示したポリマーＢ、Ｃ，Ｄ、ドの親水性ポリエ
ーテルウレタンのみを用いて実施例１と同様にして版組
成物を作成し評価した、いずれも水現象が可能であるレ
リーフであるレリーフパターンを得たがレリーフ部は、
フレキソ刷版として十分な耐水性を示さながった。Comparative Example A plate composition was prepared and evaluated in the same manner as in Example 1 using only the hydrophilic polyether urethanes of Polymers B, C, D, and Do shown in Synthesis Examples. All of them are capable of water phenomenon. I obtained a relief pattern with a relief of , but the relief part is
It did not show sufficient water resistance as a flexographic printing plate.
実施例１〜９及び比較層す版性能評価結果を表２に示す
。Examples 1 to 9 and comparative layered plate performance evaluation results are shown in Table 2.
以下余白
表１
合成ポリマーの親水基含有量
（発明の効果）
以上かかる構成より成る本発明の組成物は、親水性ポリ
エーテルウレタンと疎水性ポリマーとがブレンドされて
いるので水現像性を低下させずにしかも水系フレキソイ
ンキに対して十分耐水性を示すため、特にフレキソ印刷
版用として有用である。Table 1 below: Hydrophilic group content of synthetic polymer (effects of the invention) The composition of the present invention having the above structure has a blend of a hydrophilic polyether urethane and a hydrophobic polymer, and therefore reduces water developability. In addition, it exhibits sufficient water resistance against water-based flexographic inks, so it is particularly useful for flexographic printing plates.
特許出願人 東洋紡績株式会社Patent applicant: Toyobo Co., Ltd.
Claims (1)
５０〜９７重量％ （Ｂ）エチレン性不飽和化合物３〜５０重量％ （Ｃ）光重合開始剤０．１〜２重量％ を含有することを特徴とする感光性樹脂組成物。[Scope of Claims] (A) Hydrophilic polyether urethane and hydrophobic polymer 50-97% by weight (B) Ethylenically unsaturated compound 3-50% by weight (C) Photopolymerization initiator 0.1-2% by weight A photosensitive resin composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19733688A JPH0246460A (en) | 1988-08-08 | 1988-08-08 | Photosensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19733688A JPH0246460A (en) | 1988-08-08 | 1988-08-08 | Photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0246460A true JPH0246460A (en) | 1990-02-15 |
Family
ID=16372777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19733688A Pending JPH0246460A (en) | 1988-08-08 | 1988-08-08 | Photosensitive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0246460A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290663A (en) * | 1991-03-01 | 1994-03-01 | W. R. Grace & Co.-Conn. | Photocurable polyurethane-acrylate ionomer compositions for aqueous developable printing plates |
| JPH07219222A (en) * | 1994-01-25 | 1995-08-18 | Morton Thiokol Inc | Aqueous image-forming composition and its dry film |
| JPH07234508A (en) * | 1994-01-25 | 1995-09-05 | Morton Thiokol Inc | Aquatic optical imaging composition and dry film therefor |
| JPH07234506A (en) * | 1994-01-25 | 1995-09-05 | Morton Thiokol Inc | Aquatic optical imaging composition and dry film therefor |
| JPH07234507A (en) * | 1994-01-25 | 1995-09-05 | Morton Thiokol Inc | Aquatic optical imaging composition |
| JPH07271033A (en) * | 1994-01-25 | 1995-10-20 | Morton Thiokol Inc | Optical-image forming composition |
| US5554712A (en) * | 1992-08-28 | 1996-09-10 | W.R. Grace & Co.-Conn. | Aqueous developable photosensitive polyurethane-(meth)acrylate |
| JP2012194371A (en) * | 2011-03-16 | 2012-10-11 | Mitsubishi Paper Mills Ltd | Photosensitive lithographic printing plate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62246047A (en) * | 1986-04-18 | 1987-10-27 | Kuraray Co Ltd | Photosensitive composition |
| JPS63186232A (en) * | 1987-01-28 | 1988-08-01 | Toyobo Co Ltd | Photosensitive resin composition |
-
1988
- 1988-08-08 JP JP19733688A patent/JPH0246460A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62246047A (en) * | 1986-04-18 | 1987-10-27 | Kuraray Co Ltd | Photosensitive composition |
| JPS63186232A (en) * | 1987-01-28 | 1988-08-01 | Toyobo Co Ltd | Photosensitive resin composition |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5290663A (en) * | 1991-03-01 | 1994-03-01 | W. R. Grace & Co.-Conn. | Photocurable polyurethane-acrylate ionomer compositions for aqueous developable printing plates |
| US5554712A (en) * | 1992-08-28 | 1996-09-10 | W.R. Grace & Co.-Conn. | Aqueous developable photosensitive polyurethane-(meth)acrylate |
| JPH07219222A (en) * | 1994-01-25 | 1995-08-18 | Morton Thiokol Inc | Aqueous image-forming composition and its dry film |
| JPH07234508A (en) * | 1994-01-25 | 1995-09-05 | Morton Thiokol Inc | Aquatic optical imaging composition and dry film therefor |
| JPH07234506A (en) * | 1994-01-25 | 1995-09-05 | Morton Thiokol Inc | Aquatic optical imaging composition and dry film therefor |
| JPH07234507A (en) * | 1994-01-25 | 1995-09-05 | Morton Thiokol Inc | Aquatic optical imaging composition |
| JPH07271033A (en) * | 1994-01-25 | 1995-10-20 | Morton Thiokol Inc | Optical-image forming composition |
| JP2012194371A (en) * | 2011-03-16 | 2012-10-11 | Mitsubishi Paper Mills Ltd | Photosensitive lithographic printing plate |
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