JPH0341820B2 - - Google Patents
Info
- Publication number
- JPH0341820B2 JPH0341820B2 JP14027183A JP14027183A JPH0341820B2 JP H0341820 B2 JPH0341820 B2 JP H0341820B2 JP 14027183 A JP14027183 A JP 14027183A JP 14027183 A JP14027183 A JP 14027183A JP H0341820 B2 JPH0341820 B2 JP H0341820B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- present
- compound
- photosensitive
- sulfonic acid
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 28
- 238000009833 condensation Methods 0.000 claims description 17
- 150000002989 phenols Chemical class 0.000 claims description 12
- 239000002952 polymeric resin Substances 0.000 claims description 12
- 229920003002 synthetic resin Polymers 0.000 claims description 11
- -1 quinonediazide sulfonic acid ester Chemical class 0.000 claims description 10
- 150000003935 benzaldehydes Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920005989 resin Polymers 0.000 description 48
- 239000011347 resin Substances 0.000 description 48
- 238000007639 printing Methods 0.000 description 25
- 230000005494 condensation Effects 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 12
- 229940126062 Compound A Drugs 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 4
- 150000003459 sulfonic acid esters Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- LMWMTSCFTPQVCJ-UHFFFAOYSA-N 2-methylphenol;phenol Chemical compound OC1=CC=CC=C1.CC1=CC=CC=C1O LMWMTSCFTPQVCJ-UHFFFAOYSA-N 0.000 description 2
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- VZQBDGHUOBRFAA-UHFFFAOYSA-N 2-(2,6-dihydroxyphenyl)benzaldehyde Chemical compound C1(O)=C(C(O)=CC=C1)C1=CC=CC=C1C=O VZQBDGHUOBRFAA-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920003261 Durez Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- LEEBETSNAGEFCY-UHFFFAOYSA-N [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC(=O)C=C1 Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC(=O)C=C1 LEEBETSNAGEFCY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 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
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 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
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Description
産業上の利用分野
本発明は感光性組成物に関し、更に詳しくはイ
ンキ着肉性、現像性、レジスト強度に優れ、かつ
塗布性能も良好なｏ−キノンジアジド化合物を感
光体とするポジ型感光性組成物に関する。
従来技術
ｏ−キノンジアジド化合物とｍ−クレゾールホ
ルマリンノボラツク樹脂等の如きアルカリ可溶性
樹脂を含む感光性組成物はポジ型平版印刷版材料
として一般に知られている。また印刷版の画像部
の親油性の向上を目的として、例えばアルカリ不
溶性またはアルカリ難溶性の変性ノボラツク樹脂
あるいはこれらの樹脂とハロゲノスルホニル基を
有するｏ−キノンジアジド化合物とを縮合させた
化合物を含有せしめたポジ型平版印刷版材料も知
られている。例えばドイツ特許第2146167号明細
書、特公昭56−35854号公報に記載されているよ
うなｐ−置換フエニル・ホルマリンノボラツク樹
脂のｏ−ナフトキノンジアジドスルホン酸エステ
ルを用うる技術、さらに特開昭5o−125806号公
報に記載されているような置換フエノール類とア
ルデヒド類との縮合樹脂を用うる技術等が開示さ
れている。
また更に上記の他の親油性樹脂としては、例え
ば特開昭54−116218号、同55−127553号各公報に
は、ｐ−置換フエノールとフエノールの混合物と
ホルマリンとの縮合樹脂またはこの樹脂のｏ−ナ
フトキノンジアジドスルホン酸エステルを用い得
ることが開示されている。
しかし 上記により開示された親油性樹脂で
は、その親油化に対する効果が必ずしも充分とは
言えず、また一方上記の親油性樹脂では、疲労し
た現像液による現像性不良を起し易く、そのため
に汚れを発生させたり、濃厚現像液が使用された
場合には現像オーバーによるレジストの損失等も
発生し易く改良すべき問題が多い。
また親油性の十分な樹脂では、印刷版材料の製
造時に感光性組成物を含有する層の塗布性が良好
ではなく、例えば感光性層の塗布ムラ、塗布故障
等を起し、そのため印刷材料としての性能バラツ
キあるいは製造コストの上昇等好ましくない問題
をもたらすことになる。
発明の目的
そこで本発明の目的は、画線部の親油性が高
く、疲労現像液での汚れの発生や濃厚現像液にお
けるレジストの損失の少ない感光性組成物を提供
することにあり、また他の目的は、印刷材料製造
時における塗布性能が優れた感光性組成物を提供
することにある。
発明の構成
本発明者らが種々検討を重ねた結果、上記目的
は下記一般式〔〕で示される置換フエノール類
とベンズアルデヒド類との縮合重合樹脂のｏ−キ
ノンジアジドスルホン酸エステルを含む感光性組
成物により達成し得ることがわかつた。
一般式〔〕
式中、Ｒは炭素原子数１〜10のアルキル基また
はフエニル基を表わし、ｎは１〜３の整数を表わ
す。
すなわち、本発明の感光性組成物は、上記一般
式〔〕で示される置換フエノール類とベンズア
ルデヒド類との縮合重合樹脂のｏ−キノンジアジ
ドスルホン酸エステル（以下、本発明に係わる化
合物Ａと称す）からなる親油性樹脂を主成分とし
て含むものであり、特に縮合剤としてのベンズア
ルデヒド類の形で豊富なフエニル基を有するため
に後述の如き本発明の諸効果を発揮し得るものと
推定される。
以下、本発明を更に詳細に説明する。
先づ本発明に係わる化合物Ａの製造に用いられ
る前記一般式〔〕で示される置換フエノール類
について述べれば、一般式〔〕においてＲで表
わされる炭素原子数１〜10のアルキル基として
は、例えば直鎖状、分岐状あるいは環状のいずれ
でもよく、また置換基（好ましくはフエニル基）
を有してもよい。その具体例としてはメチル基、
エチル基、ｎ−ブチル基、ｔ−ブチル基、ペンチ
ル基、ヘキシル基、オクチル基、シクロヘキシル
基、ベンジル基等を挙げることができる。
以下に本発明に係わる一般式〔〕で示される
置換フエノール類の代表的具体例を挙げるが、本
発明はこれらのみに限定されるものではない。
化合物例
INDUSTRIAL APPLICATION FIELD The present invention relates to a photosensitive composition, and more specifically, a positive photosensitive composition using an o-quinonediazide compound as a photoreceptor, which has excellent ink receptivity, developability, and resist strength, and also has good coating performance. relating to things. Prior Art A photosensitive composition containing an o-quinonediazide compound and an alkali-soluble resin such as m-cresol formalin novolac resin is generally known as a positive-working lithographic printing plate material. In addition, for the purpose of improving the lipophilicity of the image area of the printing plate, for example, an alkali-insoluble or poorly alkali-soluble modified novolac resin or a compound obtained by condensing these resins with an o-quinonediazide compound having a halogenosulfonyl group is contained. Positive-working lithographic printing plate materials are also known. For example, the technology using o-naphthoquinonediazide sulfonic acid ester of p-substituted phenyl formalin novolak resin as described in German Patent No. 2146167 and Japanese Patent Publication No. 56-35854; A technique using a condensation resin of substituted phenols and aldehydes as described in Japanese Patent No. 125806 is disclosed. Furthermore, as other lipophilic resins mentioned above, for example, in JP-A-54-116218 and JP-A-55-127553, condensation resins of p-substituted phenols, mixtures of phenols, and formalin, or o - It is disclosed that naphthoquinonediazide sulfonic acid esters can be used. However, the lipophilic resins disclosed above cannot necessarily be said to have a sufficient effect on lipophilicity, and on the other hand, the lipophilic resins described above tend to suffer from poor developability due to a tired developer, and are therefore prone to stains. When a concentrated developer is used, resist loss due to overdevelopment is likely to occur, and there are many problems that need to be improved. In addition, with resins that are sufficiently lipophilic, the coating properties of the layer containing the photosensitive composition during the production of printing plate materials are not good, resulting in uneven coating of the photosensitive layer, coating failures, etc. This results in undesirable problems such as performance variations and increased manufacturing costs. OBJECTS OF THE INVENTION Therefore, an object of the present invention is to provide a photosensitive composition which has high lipophilicity in the image area and which causes less staining in a fatigued developer and less loss of resist in a concentrated developer. An object of the present invention is to provide a photosensitive composition with excellent coating performance during the production of printing materials. Structure of the Invention As a result of various studies by the present inventors, the above object is to provide a photosensitive composition containing an o-quinonediazide sulfonic acid ester of a condensation polymer resin of substituted phenols and benzaldehydes represented by the following general formula []. It turns out that this can be achieved by General formula [] In the formula, R represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3. That is, the photosensitive composition of the present invention is made from o-quinonediazide sulfonic acid ester (hereinafter referred to as compound A according to the present invention) of a condensation polymer resin of substituted phenols represented by the above general formula [] and benzaldehyde. It contains a lipophilic resin as a main component, and is presumed to be able to exhibit the various effects of the present invention as described below because it has an abundance of phenyl groups, especially in the form of benzaldehydes as a condensing agent. The present invention will be explained in more detail below. First, referring to the substituted phenols represented by the general formula [] used in the production of the compound A according to the present invention, the alkyl group having 1 to 10 carbon atoms represented by R in the general formula [] includes, for example, It may be linear, branched or cyclic, and a substituent (preferably a phenyl group)
It may have. Specific examples include methyl group,
Examples include ethyl group, n-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, cyclohexyl group, and benzyl group. Typical specific examples of substituted phenols represented by the general formula [] according to the present invention are listed below, but the present invention is not limited to these. Compound example
【式】【formula】
【式】【formula】
【式】【formula】
本発明においては上記例示化合物の中でｐ−ｔ
−ブチルフエノールおよびｐ−オクチルフエノー
ルが好ましく、これらの置換フエノール類は単独
であるいは混合して用いられる。
次に本発明に係わる化合物Ａの製造に縮合剤と
して用いられるベンズアルデヒド類としては、例
えばベンズアルデヒド、４−メチル−ベンズアル
デヒド、４−ｔ−ブチル−ベンズアルデヒド、４
−エチル−ベンズアルデヒド等を挙げることがで
きるが、本発明においてはベンズアルデヒドが好
ましく用いられる。
さらに前記置換フエノール類と上記ベンズアル
デヒド類との縮合重合樹脂を合成する方法につい
て述べれば、上記合成は従来公知の方法により酸
を触媒として用いて行われる。
例えば置換フエノール類１モルに対してベンズ
アルデヒド類を約0.9モルを混合し、塩酸等の触
媒を用い、60℃〜180℃で30分ないし４時間を要
して縮合重合せしめる。このようにして得られる
置換フエノール・ベンズアルデヒド縮合重合樹脂
の平均分子量（Mw）は、GPC（ポリスチレン比
較）約200ないし10000であり、好ましくは約400
ないし5000である。
上記縮合重合樹脂のｏ−キノンジアジドスルホ
ン酸エステルを合成する方法も従来公知の方法で
よく、例えば水酸基１つを有する縮合重合樹脂１
モルに対してｏ−ナフトキノンジアジドスルホニ
ルクロライド0.2ないし0.8モルをジオキサン中に
溶解せしめ、炭酸アルカリを滴下することにより
合成される。
縮合重合樹脂の反応基である水酸基に対するｏ
−ナフトキノンジアジドの縮合反応率は10〜80モ
ル％であり、好ましくは20〜60モル％、より好ま
しくは40〜55モル％である。
上記により合成される本発明に係わる化合物Ａ
は感光性組成物として単独で使用することができ
るが、本発明においては更に本発明に係わる化合
物Ａとは置換フエノール類を異にする後記の縮合
重合樹脂のｏ−キノンジアジドスルホン酸エステ
ルおよび後述の非感光性樹脂と供に併用して用い
ることが好ましい。
上記本発明に係わる化合物Ａとは異なる縮合重
合樹脂のｏ−キノンジアジドスルホン酸エステル
（以下、化合物Ｂと称す）は、従来公知のポジ型
感光剤を包含するものであり、例えば種々の脂肪
族あるいは芳香族の水酸基またはアミノ基にｏ−
ベンゾキノンジアジド、ｏ−ナフトキノンジアジ
ド等のスルホニルクロライドを反応させて合成す
ることができる。
例えばJ.Kosar著「ライト・センシテイブ・シ
ステムズ」（ジヨーン・ウイリー・アンド・サン
ズ社発刊）第332頁〜第352頁に記載されている化
合物、すなわち、ｍ−クレゾール・ホルマリンノ
ボラツク樹脂のｏ−ナフトキノンジアジドスルホ
ン酸エステル、例えば特開昭56−1044号、同56−
1045号、米国特許第3635709号等に記載のある多
価フエノールとアルデヒドまたはケトンとの縮合
樹脂のｏ−ナフトキノンジアジドスルホン酸エス
テル等が本発明において好ましく用いられる。
また前記本発明において用いられる非感光性樹
脂としてはアルカリ可溶性樹脂が好ましく用いら
れ、例えばフエノール・ホルマリンノボラツク樹
脂、クレゾール・ホルマリンノボラツク樹脂、特
開昭55−57841号記載のフエノール・クレゾール
混合のホルマリン収縮ノボラツク樹脂等のノボラ
ツク樹脂類、ならびにスチレン−無水マレイン酸
共重合体樹脂、（メタ）アクリル酸−（メタ）アク
リル酸エステル共重合体樹脂、酢酸ビニル−（メ
タ）アクリル酸共重合体樹脂、ポリ−ｐ−ヒドロ
キシスチレン樹脂等のビニル重合体樹脂等を用い
ることができる。上記各種樹脂ノ中で、クレゾー
ル・ホルマリンノボラツク樹脂が好ましく、更に
好ましくはフエノール・クレゾール混合ノボラツ
ク樹脂である。
本発明の感光性組成物に好ましく含有される本
発明に係わる化合物Ａおよび前記化合物Ｂならび
に上記非感光性樹脂の感光性組成物中での構成比
はその使用目的により異なるが、通常以下に示す
通りである。
（感光性組成物における構成比）
化合物Ａ；0.1〜20重量％、好ましくは１〜10重
量％、
化合物Ｂ；５〜80重量％、好ましくは10〜60重量
％、
非感光性樹脂；10〜90重量％、好ましくは20〜80
重量％、
上記のような構成になる本発明の感光性組成物
は、必要に応じてその他種々の添加剤を加えるこ
とができる。
例えば感光性組成物に可視的感光性を与えるた
めに、トリフエニルメタン染料、シアニン染料、
ジアゾ染料、スチリル染料等の染料を始めとして
銅フタロシアニン等の顔料等を加えることができ
る。また塗布性を改良する目的でセルロースアル
キルエーテル、フツ素系界面活性剤、エチレンオ
キサイド系界面活性剤、さらに塗膜の物性改良剤
としてのリン酸エステル、フタル酸エステル等の
可塑剤を添加してもよく、さらに増感剤としての
無水グルタル酸、無水テトラヒドロフタル酸の如
き酸無水物、焼き出し画像を得ることを目的とし
て光によるルイス酸発生剤、例えばｏ−ナフトキ
ノンジアジド−４−スルホニルクロライド、ｏ−
ナフトキノンジアジド−４−スルホン酸エステ
ル、無機の対イオンを持つジアゾニウム塩、フリ
ーラジカル発生剤であるトリハロメチル化合物等
を添加することもできる。
上記添加剤の使用量は、添加剤の種類あるいは
目的等によつて若干異なるが、一般的には感光性
組成物に対して0.01〜20重量％程度である。
本発明の感光性組成物を平版印刷材料用の支持
体上に塗設するには、該組成物の溶媒、例えばメ
チルまたはエチルセロソルブ、メチルまたはエチ
ルセロソルブアセテート、ジメチルホルムアミ
ド、ジメチルスルホキシド、ジオキサン、アセト
ン、トリクロルエタン等の溶媒に溶解してからア
ルミ板、亜鉛板、プラスチツクフイルム、クロム
メツキした鉄板、クロムメツキしたアルミ板の如
き支持体上に塗布し、乾燥して平版印刷版材料と
なし、種々の用途に供せられる。
特に本発明の感光性組成物が平版印刷版材料と
して供せられる場合には、砂目立てしたアルミニ
ウム板、砂目立てした後陽極酸化したアルミニウ
ム板、クロムメツキした鉄板等が支持体として好
ましく用いられる。特に砂目立てした後陽極酸化
したアルミニウム板の使用が最も好ましい。
感光性組成物を支持体上に塗布する方法として
は、例えばロールコーター法、ダブルロールコー
ター法、ワイヤーバーコーター法およびビードコ
ーター法等を挙げることができる。
塗布後の乾燥条件としては、室温から約100℃
程度で５分ないし数時間が適切である。
このようにして製られた本発明に係わる平版印
刷材料の使用に際しては、従来公知の方法が適用
され、水銀灯、メタルハライドランプ等で露光
し、メタケイ酸ソーダ、リン酸ソーダ等のアルカ
リ水溶液を用いて現像を行い、印刷版として提供
される。
以下に本発明に係わる化合物Ａの合成法を例示
する。
合成例 １
住友デユレズ(株)製のスミライトレジン“SK−
134”〔ｐ−ｔ−ブチルフエノール・ベンズアルデ
ヒド樹脂（分子量約1000）〕100ｇ、ｏ−ナフトキ
ノンジアジド−５−スルホン酸クロライド56ｇを
ジオキサン800mlに溶かし、40〜50℃に加温し、
炭酸カリ水溶液（15％）を125ml徐々に滴下する。
滴下終了後、約１時間反応させ、反応液を濾過し
た後、塩酸を含む多量の水中に投下し、樹脂を折
出させる。これを濾過乾燥させると120ｇのｏ−
ナフトキノンジアジドスルホン酸エステル樹脂が
得られた。
合成例 ２
ｐ−ｔ−ブチルフエノール140ｇと４−メチル
ベンズアルデヒド110ｇをエタノール300mlに溶か
し、35％塩酸0.5ｇ、濃硫酸0.5ｇを加え、還流下
３時間反応させた後、多量の水中に投下し、205
ｇの樹脂を得た。
上記樹脂100ｇを用いて合成例１と同様に縮合
反応を行わせ、ｏ−ナフトキノンジアジドスルホ
ン酸エステル樹脂118ｇを得た。
合成例 ３
ｐ−オクチルフエノール192ｇとベンズアルデ
ヒド100ｇをイソプロパノール500mlに溶かし、35
％塩酸0.5ｇ、濃硫酸0.5ｇを加え、還流下４時間
反応させた後、多量の水中に投下し、240ｇの樹
脂を得た。
上記樹脂100ｇとｏ−ナフトキノンジアジド−
５−スルホニルクロライド46ｇをジオキサン800
mlに溶かし、合成例１と同様に縮合反応を行わせ
た。かくしてｏ−ナフトキノンジアジドスルホン
酸エステル樹脂110ｇが得られた。
以下、実施例を挙げて本発明を具体的に記載す
るが、本発明はこれらのみに限定されるものでは
ない。
実施例 １
電解研摩法により砂目立てし、さらに陽極酸化
した厚さ0.24mmのアルミニウム板に下記組成の感
光液をダブルローラーコーターによつて塗布し、
40〜60℃で約２分間、そして100℃で約４分間乾
燥を行ない、平版印刷版材料（試料１）を製作し
た。
（感光液組成）
前記合成例１により合成された樹脂 0.08重量部
ｏ−ナフトキノンジアジド−５−スルホニルクロ
ライドとレゾルシン・ベンズアルデヒド樹脂の縮
合物（特開昭56−1044号記載の化合物で縮合率50
モル％） 1.0重量部
フエノール：ｍ−クレゾール：ｐ−クレゾール
（モル比が３：４：３）のフエノールクレゾー
ル・ホルムアルデヒド樹脂（特開昭55−57841号
記載の化合物） 3.0重量％
ｐ−ジアゾジフエニルアミンのヘキサフルオロホ
スフエート塩 0.04重量部
ビクトリアピユアブル−BOH（保土ケ谷化学(株)
製） 0.04重量部
無水グルタル酸 0.03重量部
メチルセロソルブ 30重量部
この印刷材料の乾燥後の塗膜重量は2.5ｇ／m2
であつた。塗膜は均一で、スジムラ、乾燥ムラ、
ギヤーマーク、ローラーマーク、ハジキ等の塗布
欠陥はみられなかつた。
上記により得られた感光性平版印刷材料に網点
写真のポジ原稿およびコダツクステツプタブレツ
トNo.２を密着して2KWメタルハライドランプ
（ウシオ電機(株)社製）を用いて距離１ｍにて100秒
露光を与えた。この露光済み印刷材料をさくら
PS版用現像液SDp−１の７倍希釈液、４倍希釈
液で25℃で45秒間現像処理を行つた。
現像により形成された平版印刷版の画像部は親
油性に富み、水に対する接触角は90°以上を示し
た。
上記の４倍希釈液という濃厚な現像液でオーバ
ー現像処理を行つた平版印刷版においても画像部
のレジストの損失はほとんど観察されなかつた。
次に上記の７倍希釈の現像液に全面露光した平
版印刷材料を現像液１当り2.5m2の割合で浸漬
し、現像させて現像液を疲労せしめ、再度ポジ原
稿を密着露光した印刷材料を現像処理した。露光
部すなわち非画像部の現像不良の有無をチエツク
するための現像インキをインキ盛り（さくらPS
版現像インキSpo−１）して観察したが汚れは認
められなかつた。
次にこの印刷版をガム引処理（サクラPS版ガ
ム液SGU−１）後、オフセツト印刷機“小森ス
プリントＬ−25B”にセツトし、東華色素(株)製印
刷インキ、スーパーグロリアSGを用いて印刷を
行つた。その結果、印刷初期においてもインキ着
肉性の優れた印刷物を得ることができた。
比較試料１
実施例１における本発明に係わる感光液に、合
成例１による樹脂の代りにｐ−ｔ−ブチルフエノ
ール・ホルマリンノボラツク樹脂（群栄化学(株)
製、PP−3121分子量約1000）を用いて実施例１
と同様の実験を行ない、得られた結果を下記表１
に記載した。
（比較試料２）
実施例１における本発明に係わる感光液に、合
成例１による樹脂の代りにｐ−ｔ−ブチルフエノ
ール・ホルマリンノボラツク樹脂のｏ−ナフトキ
ノンジアジド−５−スルホン酸エステル（縮合率
50モル％）を用いて実施例１と同様の実験を行な
い、得られた結果を下記表１に示した。
（比較試料３）
実施例１における本発明に係わる感光液に、合
成例１による樹脂の代りにｐ−フエニルフエノー
ル・ホルマリンノボラツク樹脂（分子量約1000）
のｏ−ナフトキノンジアジド−５−スルホン酸エ
ステル（縮合率50モル％）を用いて実施例１と同
様の実験を行ない、得られた結果を下記表１に示
した。尚、下記表において試料２〜４は上記比較
試料１〜３を示し、また◎印は非常に優れてい
る、○印は優れている、△印はやゝ劣る、×印は
劣ることを意味する。 In the present invention, among the above-mentioned exemplified compounds, p-t
-Butylphenol and p-octylphenol are preferred, and these substituted phenols may be used alone or in combination. Next, the benzaldehydes used as a condensing agent in the production of compound A according to the present invention include, for example, benzaldehyde, 4-methyl-benzaldehyde, 4-t-butyl-benzaldehyde, 4-t-butyl-benzaldehyde,
Examples include -ethyl-benzaldehyde, and benzaldehyde is preferably used in the present invention. Furthermore, to describe a method for synthesizing a condensation polymer resin of the substituted phenols and the benzaldehydes, the synthesis is carried out by a conventionally known method using an acid as a catalyst. For example, about 0.9 mole of benzaldehyde is mixed with 1 mole of substituted phenol, and condensation polymerization is carried out at 60 DEG C. to 180 DEG C. for 30 minutes to 4 hours using a catalyst such as hydrochloric acid. The average molecular weight (Mw) of the substituted phenol-benzaldehyde condensation polymer resin thus obtained is about 200 to 10,000 GPC (compared to polystyrene), preferably about 400.
to 5,000. The method for synthesizing the o-quinonediazide sulfonic acid ester of the above condensation polymer resin may also be a conventionally known method, for example, condensation polymer resin 1 having one hydroxyl group.
It is synthesized by dissolving 0.2 to 0.8 moles of o-naphthoquinonediazide sulfonyl chloride in dioxane and adding alkali carbonate dropwise. o for the hydroxyl group which is the reactive group of the condensation polymer resin
- The condensation reaction rate of naphthoquinone diazide is 10 to 80 mol%, preferably 20 to 60 mol%, more preferably 40 to 55 mol%. Compound A according to the present invention synthesized by the above method
can be used alone as a photosensitive composition, but in the present invention, the o-quinonediazide sulfonic acid ester of the condensation polymer resin described below and the below-mentioned It is preferable to use it in combination with a non-photosensitive resin. The o-quinonediazide sulfonic acid ester (hereinafter referred to as compound B) of a condensation polymer resin different from compound A according to the present invention includes conventionally known positive photosensitive agents, such as various aliphatic or o- to the aromatic hydroxyl group or amino group
It can be synthesized by reacting sulfonyl chlorides such as benzoquinonediazide and o-naphthoquinonediazide. For example, the compound described in "Light Sensitive Systems" by J. Kosar (published by John Willey & Sons), pages 332 to 352, namely, the o-cresol formalin novolak resin. Naphthoquinone diazide sulfonic acid ester, e.g. JP-A-56-1044, JP-A-56-1044;
O-naphthoquinonediazide sulfonic acid esters of condensation resins of polyhydric phenols and aldehydes or ketones, as described in No. 1045, US Pat. No. 3,635,709, etc., are preferably used in the present invention. As the non-photosensitive resin used in the present invention, alkali-soluble resins are preferably used, such as phenol-formalin novolak resin, cresol-formalin novolak resin, and the phenol-cresol mixed resin described in JP-A-55-57841. Novolac resins such as formalin-shrinkable novolac resins, styrene-maleic anhydride copolymer resins, (meth)acrylic acid-(meth)acrylic acid ester copolymer resins, vinyl acetate-(meth)acrylic acid copolymer resins , vinyl polymer resin such as poly-p-hydroxystyrene resin, etc. can be used. Among the various resins mentioned above, cresol/formalin novolak resin is preferred, and phenol/cresol mixed novolak resin is more preferred. The composition ratio of the compound A of the present invention, the compound B, and the non-photosensitive resin preferably contained in the photosensitive composition of the present invention varies depending on the purpose of use, but is usually as shown below. That's right. (Composition ratio in photosensitive composition) Compound A: 0.1 to 20% by weight, preferably 1 to 10% by weight, Compound B: 5 to 80% by weight, preferably 10 to 60% by weight, Non-photosensitive resin; 10 to 10% by weight. 90% by weight, preferably 20-80
Weight %: The photosensitive composition of the present invention having the above-mentioned structure may contain various other additives as required. For example, triphenylmethane dyes, cyanine dyes,
In addition to dyes such as diazo dyes and styryl dyes, pigments such as copper phthalocyanine can be added. In addition, to improve coating properties, cellulose alkyl ethers, fluorine surfactants, ethylene oxide surfactants, and plasticizers such as phosphate esters and phthalate esters are added to improve the physical properties of the coating film. Furthermore, acid anhydrides such as glutaric anhydride and tetrahydrophthalic anhydride as sensitizers, and photo-induced Lewis acid generators such as o-naphthoquinonediazide-4-sulfonyl chloride for the purpose of obtaining printed images. o-
Naphthoquinonediazide-4-sulfonic acid ester, diazonium salt having an inorganic counter ion, trihalomethyl compound which is a free radical generator, etc. can also be added. The amount of the additive used varies slightly depending on the type or purpose of the additive, but is generally about 0.01 to 20% by weight based on the photosensitive composition. For coating the photosensitive compositions of the invention on supports for lithographic printing materials, the solvents of the compositions, such as methyl or ethyl cellosolve, methyl or ethyl cellosolve acetate, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, can be used. After dissolving in a solvent such as trichloroethane, it is applied onto a support such as an aluminum plate, zinc plate, plastic film, chrome-plated iron plate, or chrome-plated aluminum plate, and dried to form a lithographic printing plate material for various uses. It is offered to In particular, when the photosensitive composition of the present invention is used as a lithographic printing plate material, grained aluminum plates, grained and anodized aluminum plates, chrome-plated iron plates, etc. are preferably used as the support. In particular, it is most preferable to use an aluminum plate that has been grained and then anodized. Examples of methods for applying the photosensitive composition onto the support include a roll coater method, a double roll coater method, a wire bar coater method, and a bead coater method. Drying conditions after application are from room temperature to approximately 100℃.
5 minutes to several hours is appropriate. When using the lithographic printing material according to the present invention produced in this way, a conventionally known method is applied, such as exposure with a mercury lamp, metal halide lamp, etc., and using an alkaline aqueous solution such as sodium metasilicate or sodium phosphate. It is developed and provided as a printing plate. The method for synthesizing compound A according to the present invention will be illustrated below. Synthesis example 1 Sumilite resin “SK-” manufactured by Sumitomo Durez Co., Ltd.
134" [100 g of pt-butylphenol benzaldehyde resin (molecular weight approximately 1000)] and 56 g of o-naphthoquinonediazide-5-sulfonic acid chloride were dissolved in 800 ml of dioxane and heated to 40 to 50°C.
Gradually add 125 ml of potassium carbonate aqueous solution (15%) dropwise.
After the dropwise addition is completed, the reaction is allowed to proceed for about 1 hour, and the reaction solution is filtered and then poured into a large amount of water containing hydrochloric acid to precipitate the resin. When this is filtered and dried, 120g of o-
A naphthoquinonediazide sulfonic acid ester resin was obtained. Synthesis Example 2 140 g of pt-butylphenol and 110 g of 4-methylbenzaldehyde were dissolved in 300 ml of ethanol, 0.5 g of 35% hydrochloric acid and 0.5 g of concentrated sulfuric acid were added, the mixture was reacted under reflux for 3 hours, and then poured into a large amount of water. , 205
g of resin was obtained. A condensation reaction was carried out in the same manner as in Synthesis Example 1 using 100 g of the above resin to obtain 118 g of o-naphthoquinonediazide sulfonic acid ester resin. Synthesis Example 3 Dissolve 192 g of p-octylphenol and 100 g of benzaldehyde in 500 ml of isopropanol,
After adding 0.5 g of % hydrochloric acid and 0.5 g of concentrated sulfuric acid and reacting under reflux for 4 hours, the mixture was poured into a large amount of water to obtain 240 g of resin. 100g of the above resin and o-naphthoquinonediazide
46 g of 5-sulfonyl chloride and 800 g of dioxane
ml, and a condensation reaction was carried out in the same manner as in Synthesis Example 1. Thus, 110 g of o-naphthoquinonediazide sulfonic acid ester resin was obtained. EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these. Example 1 A photosensitive solution having the following composition was applied using a double roller coater to a 0.24 mm thick aluminum plate that had been grained using an electrolytic polishing method and further anodized.
Drying was carried out at 40 to 60°C for about 2 minutes and at 100°C for about 4 minutes to produce a lithographic printing plate material (Sample 1). (Photosensitive liquid composition) Resin synthesized in Synthesis Example 1 0.08 parts by weight Condensate of o-naphthoquinonediazide-5-sulfonyl chloride and resorcinol benzaldehyde resin (condensation rate 50 with the compound described in JP-A-56-1044)
(mol%) 1.0 parts by weight Phenol:m-cresol:p-cresol (mole ratio 3:4:3) Phenol-cresol formaldehyde resin (compound described in JP-A-55-57841) 3.0 parts by weight p-diazodif Hexafluorophosphate salt of enylamine 0.04 parts by weight Victoria Pure Blue-BOH (Hodogaya Chemical Co., Ltd.)
0.04 parts by weight Glutaric anhydride 0.03 parts by weight Methyl cellosolve 30 parts by weight The coating weight of this printing material after drying is 2.5 g/m 2
It was hot. The coating film is uniform, with no streaks, uneven drying,
No coating defects such as gear marks, roller marks, or cissing were observed. A positive halftone original and Kodak Step Tablet No. 2 were brought into close contact with the photosensitive lithographic printing material obtained above, and a 2KW metal halide lamp (manufactured by Ushio Inc.) was used at a distance of 1 m for 100 m. A second exposure was given. Sakura this exposed printing material
Development was performed at 25° C. for 45 seconds using a 7-fold dilution and a 4-fold dilution of PS plate developer SDp-1. The image area of the lithographic printing plate formed by development was rich in lipophilicity, and the contact angle with water was 90° or more. Almost no loss of resist in the image area was observed even in the lithographic printing plate which was over-developed with the above-mentioned 4-fold diluted developer. Next, the lithographic printing material fully exposed to the above 7-fold diluted developer was immersed at a ratio of 2.5 m 2 per developer, and the developer was exhausted by development. Developed. Apply developing ink (Sakura PS
The plate development ink Spo-1) was observed, but no stains were observed. Next, this printing plate was subjected to gumming treatment (Sakura PS version gum liquid SGU-1), then set in an offset printing machine "Komori Sprint L-25B", and printed using Super Gloria SG, a printing ink manufactured by Toka Shiki Co., Ltd. I did the printing. As a result, it was possible to obtain printed matter with excellent ink receptivity even in the initial stage of printing. Comparative Sample 1 In the photosensitive liquid according to the present invention in Example 1, pt-butylphenol formalin novolak resin (Gun-ei Chemical Co., Ltd.) was added instead of the resin according to Synthesis Example 1.
Example 1 using PP-3121 (molecular weight approximately 1000)
The results obtained are shown in Table 1 below.
Described in. (Comparative sample 2) O-naphthoquinonediazide-5-sulfonic acid ester (condensation rate
The same experiment as in Example 1 was conducted using 50 mol %), and the obtained results are shown in Table 1 below. (Comparative Sample 3) In the photosensitive liquid according to the present invention in Example 1, p-phenylphenol formalin novolak resin (molecular weight about 1000) was added instead of the resin according to Synthesis Example 1.
The same experiment as in Example 1 was conducted using o-naphthoquinonediazide-5-sulfonic acid ester (condensation rate: 50 mol%), and the results obtained are shown in Table 1 below. In addition, in the table below, Samples 2 to 4 indicate the above comparative samples 1 to 3, and the ◎ mark means very good, the ○ mark means excellent, the △ mark means slightly inferior, and the × mark means inferior. do.
【表】
上記表の結果からも明らかなように、本発明に
係わる化合物Ａを印刷材料の感光性組成物として
用いた試料１は塗布ムラもみられず、また疲労現
像液によつて生起する現像不良もなく、さらにオ
ーバー現像に際してもレジストの損失もほとんど
なく、印刷に際しての着肉性も優つている。
これに対して試料２、３および４（比較試料１、
２および３に該当）では、仮りにインキ着肉性が
優れているものは塗布性や現像性に劣つていた
り、塗布性が良好であるものはインキ着肉性、レ
ジスト強度に劣つていたりして満足し得るもので
はない。
また置換フエノール・アルデヒド類縮合重合樹
脂の組成が本発明とは異なる組成である試料４で
は樹脂中のフエニル基を増加させたにも拘わらず
塗布性および現像性が悪く、依然として問題があ
ることもわかつた。
実施例 ２
実施例１における本発明に係わる感光液に、合
成例１による樹脂の代りに合成例２の樹脂を使用
して実施例１と同様の実験を行つた結果、インキ
着肉性の優れた印刷版を得ることができた。
実施例 ３
実施例１における本発明に係わる感光液に、合
成例１による樹脂の代りに合成例３による樹脂を
用い、またメチルセロソルブの代りにエチルセロ
ソルブを使用して実施例１と同様の実験を行なつ
たところ塗布性およびインキ着肉性に優れた平版
印刷版を得ることができた。
発明の効果
本発明に係わる化合物Ａを含む感光性組成物を
用いた平版印刷材料は、塗布性に優れ、また現像
性、レジスト強度に優れるばかりでなく、インキ
着肉性も著るしく改良される。[Table] As is clear from the results in the table above, Sample 1, in which Compound A according to the present invention was used as a photosensitive composition for printing materials, showed no coating unevenness, and also showed that no unevenness was observed in the development caused by a fatigued developer. There are no defects, there is almost no loss of resist even during overdevelopment, and the ink receptivity during printing is excellent. In contrast, samples 2, 3, and 4 (comparative sample 1,
2 and 3), if the ink receptivity is excellent, the coatability and developability are poor, and the coatability is good but the ink receptivity and resist strength are poor. It's not something you can be satisfied with. In addition, Sample 4, in which the composition of the substituted phenol/aldehyde condensation polymer resin is different from that of the present invention, has poor coating properties and developability despite increasing the phenyl groups in the resin, and still has problems. I understand. Example 2 An experiment similar to Example 1 was conducted using the resin of Synthesis Example 2 instead of the resin of Synthesis Example 1 in the photosensitive liquid according to the present invention in Example 1. As a result, excellent ink receptivity was obtained. I was able to obtain a printed version. Example 3 An experiment similar to Example 1 was carried out using the resin according to Synthesis Example 3 instead of the resin according to Synthesis Example 1 and using ethyl cellosolve instead of methyl cellosolve in the photosensitive liquid according to the present invention in Example 1. As a result, a lithographic printing plate with excellent coating properties and ink receptivity was obtained. Effects of the Invention A lithographic printing material using a photosensitive composition containing the compound A according to the present invention not only has excellent coatability, developability and resist strength, but also has significantly improved ink receptivity. Ru.
Claims (1)
類とベンズアルデヒド類との縮合重合樹脂のｏ−
キノンジアジドスルホン酸エステルを含むことを
特徴とする感光性組成物。 一般式〔〕 （式中、Ｒは炭素原子数１〜10のアルキル基また
はフエニル基を表わし、ｎは１〜３の整数を表わ
す。）[Claims] 1. An o-condensation polymer resin of substituted phenols and benzaldehydes represented by the following general formula []
A photosensitive composition comprising a quinonediazide sulfonic acid ester. General formula [] (In the formula, R represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 3.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14027183A JPS6031138A (en) | 1983-07-30 | 1983-07-30 | Photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14027183A JPS6031138A (en) | 1983-07-30 | 1983-07-30 | Photosensitive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6031138A JPS6031138A (en) | 1985-02-16 |
| JPH0341820B2 true JPH0341820B2 (en) | 1991-06-25 |
Family
ID=15264888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14027183A Granted JPS6031138A (en) | 1983-07-30 | 1983-07-30 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6031138A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62161146A (en) * | 1986-01-10 | 1987-07-17 | Mitsubishi Petrochem Co Ltd | Photoresist composition |
| JPH0656487B2 (en) * | 1986-05-02 | 1994-07-27 | 東京応化工業株式会社 | Composition for positive photoresist |
| JPH0654387B2 (en) * | 1986-05-02 | 1994-07-20 | 東京応化工業株式会社 | Positive photoresist composition |
| JPH0654388B2 (en) * | 1986-05-02 | 1994-07-20 | 東京応化工業株式会社 | Positive photoresist composition |
| JPH0293651A (en) * | 1988-09-30 | 1990-04-04 | Fuji Photo Film Co Ltd | Positive type photoresist composition |
| JPH0296164A (en) * | 1988-10-03 | 1990-04-06 | Konica Corp | Photosensitive composition |
| DE69032873T2 (en) * | 1989-09-08 | 1999-07-29 | Olin Microelectronic Chemicals, Inc., Norwalk, Conn. | Radiation sensitive compositions containing fully substituted Novalak polymers |
-
1983
- 1983-07-30 JP JP14027183A patent/JPS6031138A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6031138A (en) | 1985-02-16 |
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