JPH0247738B2 - KANKOSEIJUSHISOSEIBUTSU - Google Patents
KANKOSEIJUSHISOSEIBUTSUInfo
- Publication number
- JPH0247738B2 JPH0247738B2 JP11986882A JP11986882A JPH0247738B2 JP H0247738 B2 JPH0247738 B2 JP H0247738B2 JP 11986882 A JP11986882 A JP 11986882A JP 11986882 A JP11986882 A JP 11986882A JP H0247738 B2 JPH0247738 B2 JP H0247738B2
- Authority
- JP
- Japan
- Prior art keywords
- present
- water
- photosensitive
- latex polymer
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 44
- 239000004816 latex Substances 0.000 claims description 35
- 229920000126 latex Polymers 0.000 claims description 35
- 125000002091 cationic group Chemical group 0.000 claims description 29
- 239000011342 resin composition Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 14
- 239000007788 liquid Chemical group 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000002940 repellent Effects 0.000 claims description 3
- 239000005871 repellent Substances 0.000 claims description 3
- 229920003176 water-insoluble polymer Polymers 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 23
- 239000000178 monomer Substances 0.000 description 15
- -1 hexafluorophosphate Chemical compound 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000007639 printing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid 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
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- G03F7/016—Diazonium salts or compounds
- G03F7/021—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders
- G03F7/0212—Macromolecular diazonium compounds; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the diazo resins or the polymeric diazonium compounds
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
Description
【発明の詳細な説明】
本発明は、水現像可能な感光性樹脂組成物に関
する。さらに詳しくは、高感度であつて保存安定
性にもすぐれており、かつ処理性の良い水現像が
可能である平版印刷版等に適用できる感光性樹脂
組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-developable photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition that is highly sensitive, has excellent storage stability, and can be applied to lithographic printing plates and the like that can be developed with water with good processability.
従来、水のみで現像できる平版印刷版の感光性
樹脂組成物については数多くのものが知られてい
る。例えば、特開昭52―2520号公報記載のごと
く、アクリル系ラテツクス重合体と感光性樹脂化
合物の感光性樹脂組成物がある。しかしながら、
このものは、湿気の影響で、ラテツクス重合体が
粘着性を帯びて融着を起こしやすく、保存安定性
が悪いという欠点があつた。 Conventionally, many photosensitive resin compositions for lithographic printing plates that can be developed with water only are known. For example, there is a photosensitive resin composition of an acrylic latex polymer and a photosensitive resin compound, as described in JP-A-52-2520. however,
This product had the disadvantage that the latex polymer became sticky due to the influence of moisture and was prone to fusion, resulting in poor storage stability.
また、特開昭53―145706号公報記載のごとく、
感光層を２層構成にし、下層に水溶性感光層を、
その上に水浸透性であつて親油性水不溶性の感光
層を設けた、画像形成材料の感光性樹脂組成物層
がある。この技術は上層の水浸透に時間がかかる
ため、処理操作の迅速化が困難である欠点があつ
た。 Also, as described in Japanese Patent Application Laid-Open No. 53-145706,
The photosensitive layer has a two-layer structure, and the lower layer is a water-soluble photosensitive layer.
There is a photosensitive resin composition layer of the image-forming material, on which is provided a water-permeable, lipophilic, water-insoluble photosensitive layer. This technique had the disadvantage that it was difficult to speed up the treatment operation because it took time for water to penetrate into the upper layer.
また、特開昭55―159433号公報記載の如く、若
干水溶性の感光性ジアゾ樹脂化合物と液状エポキ
シ樹脂化合物を含む感光性樹脂組成物が知られて
いる。これは若干の水溶性（ジアゾ樹脂）と液状
のエポキシ樹脂との組合せにより水現像性を付与
しているものであり、この感光性樹脂組成物は、
水溶性の乏しい素材を用いているため、もともと
現像性が悪く、長期間の保存中に、経時的に現像
性が低下して使用困難になるという不都合があつ
た。 Furthermore, as described in JP-A-55-159433, a photosensitive resin composition containing a slightly water-soluble photosensitive diazo resin compound and a liquid epoxy resin compound is known. This photosensitive resin composition has water developability due to a combination of a slightly water-soluble (diazo resin) and a liquid epoxy resin.
Because it uses a material with poor water solubility, it has poor developability, and during long-term storage, the developability deteriorates over time, making it difficult to use.
本発明はこれらの問題点を改良すべくなされた
ものであつて、本発明の目的は、高感度であり、
かつ保存安定性にすぐれた水現像可能な感光層が
得られる感光性樹脂組成物を提供することにあ
る。 The present invention has been made to improve these problems, and the purpose of the present invention is to provide high sensitivity,
Another object of the present invention is to provide a photosensitive resin composition from which a water-developable photosensitive layer with excellent storage stability can be obtained.
本発明のさらに別の目的は、処理性にすぐれた
水現像が可能な感光層が得られる感光性樹脂組成
物を提供することにある。 Still another object of the present invention is to provide a photosensitive resin composition from which a water-developable photosensitive layer with excellent processability can be obtained.
本発明の上記諸目的は、感光性ジアゾ樹脂化合
物、４級窒素原子を有するカチオン性ラテツクス
重合体、および液状の親油性水不溶性ポリマーを
含み、露光域において前記感光性ジアゾ樹脂化合
物と前記カチオンの反応により硬化し、親水性を
失い、撥水性となることを特徴とする感光性樹脂
組成物によつて達成される。 The above-mentioned objects of the present invention include a photosensitive diazo resin compound, a cationic latex polymer having a quaternary nitrogen atom, and a liquid lipophilic water-insoluble polymer. This is achieved by a photosensitive resin composition that is cured by reaction, loses hydrophilicity, and becomes water repellent.
本発明に係る感光性樹脂組成物は、支持体上に
塗設することによつて感光層を構成して、平版印
刷版等の画像形成材料とするのに用いるのに適切
である。 The photosensitive resin composition according to the present invention is suitable for forming a photosensitive layer by coating it on a support and using it as an image forming material such as a lithographic printing plate.
以下、本発明について詳述する。 The present invention will be explained in detail below.
本発明に用いられる感光性ジアゾ樹脂化合物と
しては、米国特許第2063631号および同第2667415
号の各明細書に開示のジアゾニウム塩とアルドー
ルやアセタールのような反応性カルボニル基を含
有する有機縮合剤との反応生成物、またこれらの
水溶性化合物を特開昭54―98613号公報に開示さ
れた方法によりBF4 -、PF6 -、SiF6 --、SbF6 -、
BeF4 --なるアニオン成分で置換したハロゲン化
ルイス酸塩が含まれる。特に好ましくは、ｐ―ジ
アゾジフエニルアミンとホルムアルデヒドとの重
縮合物である。これは下記一般式で表わされるモ
ノマー単位を有すると考えられている。 As the photosensitive diazo resin compound used in the present invention, US Pat.
The reaction products of diazonium salts and organic condensing agents containing reactive carbonyl groups such as aldols and acetals, as disclosed in the specifications of the above issues, and the water-soluble compounds thereof are disclosed in JP-A-54-98613. BF 4 - , PF 6 - , SiF 6 -- , SbF 6 - ,
It includes a halogenated Lewis acid salt substituted with an anion component of BeF 4 -- . Particularly preferred is a polycondensate of p-diazodiphenylamine and formaldehyde. It is believed to have a monomer unit represented by the following general formula.
ここにＸ
はハライド、スルフエート、フルオ
ロボレート、ヘキサフルオロホスフエート等のア
ニオンである。 Here, X is an anion such as halide, sulfate, fluoroborate, hexafluorophosphate, etc.
本発明に用いられる４級窒素原子を有する重合
体はラテツクス重合体（以下、本発明のカチオン
性ラテツクス重合体という。）に限られる。すな
わち、水ないしは極性溶剤に分散された粒状重合
体のみが本発明に効果的に用いられる。上記の４
級窒素原子を有するカチオン性のラテツクス重合
体がラテツクス状でなく溶液となるものである
と、感光性ジアゾ樹脂化合物との光硬化は起こる
が、硬化皮膜強度が弱く、感度も低いため、本発
明の用途として用いても性能が不十分である。 The polymer having a quaternary nitrogen atom used in the present invention is limited to a latex polymer (hereinafter referred to as the cationic latex polymer of the present invention). That is, only particulate polymers dispersed in water or polar solvents can be effectively used in the present invention. 4 above
If the cationic latex polymer having class nitrogen atoms is not in the form of a latex but in the form of a solution, photocuring with the photosensitive diazo resin compound will occur, but the cured film strength will be weak and the sensitivity will be low. The performance is insufficient even when used for this purpose.
本発明のカチオン性ラテツクス重合体として
は、ラテツクス重合体の側鎖に４級窒素原子を含
むものが好ましい。かかるラテツクス重合体を形
成するモノマー単位の代表例としては、下記一般
式〔〕〜一般式〔〕で示されるものがある。 The cationic latex polymer of the present invention preferably contains a quaternary nitrogen atom in the side chain of the latex polymer. Representative examples of monomer units forming such latex polymers include those represented by the following general formulas [] to [].
一般式〔〕
一般式〔〕
一般式〔〕
一般式〔〕
一般式〔〕
一般式〔〕〜〔〕において、Ｘ
はアニオ
ンを表わす。すなわちハロゲンイオン、硫酸イオ
ン、リン酸イオン、スルホン酸イオン、酢酸イオ
ン等である。Ｎ
に結合するＲは同一であつても
異種のものでもよく、各Ｒは水素原子又は１〜10
個の炭素原子を有するアルキル基（例えばメチ
ル、エチル、プロピル、イソブチル、ペンチル、
ヘキシル、ヘプチル、デシルの各基）、アルケニ
ル基（例えばブロペニル、ブチニルの各基）、又
は６〜20個の炭素原子を有するアリール基（例え
ばフエニル、ナフチルの各基）、アルアルキル基
（例えばベンジル、フエネチル、ナフチルメチル
の各基）、もしくはアルカリール基（例えばトリ
ル、キシリルの各基）を表わす。Ｚは不飽和複素
環を形成するのに必要な非金属原子群を表わし、
好ましくはイミダゾール、ピリジン、ピペリジ
ン、ピロールまたはモルホリン環である。ｎは整
数を表わす。 General formula [] General formula [] General formula [] General formula [] General formula [] In the general formulas [] to [], X represents an anion. That is, halogen ions, sulfate ions, phosphate ions, sulfonate ions, acetate ions, etc. The Rs bonded to N may be the same or different, and each R may be a hydrogen atom or 1 to 10
Alkyl groups having 5 carbon atoms (e.g. methyl, ethyl, propyl, isobutyl, pentyl,
hexyl, heptyl, decyl), alkenyl groups (e.g. propenyl, butynyl), or aryl groups having 6 to 20 carbon atoms (e.g. phenyl, naphthyl), aralkyl groups (e.g. benzyl), , phenethyl, naphthylmethyl groups), or alkaryl groups (for example, tolyl and xylyl groups). Z represents a group of nonmetallic atoms necessary to form an unsaturated heterocycle,
Preferred are imidazole, pyridine, piperidine, pyrrole or morpholine rings. n represents an integer.
本発明のカチオン性ラテツクス重合体を形成す
る上記カチオン性モノマーは、水溶性の調節のた
めに非カチオン性モノマーと共重合体を形成する
ことが好ましい。そのような非カチオン性モノマ
ーとしては、アクリル酸、メタクリル酸のエステ
ル、スチレン、アルキレン、エーテル、酢酸ビニ
ル、アクリロニトリル等があげられる。また、本
発明のカチオン性ラテツクス重合体は、好ましく
はジビニルベンゼンやジメタクリレート等の２個
以上の官能基を持つモノマーにより架橋され、乳
化重合により製造されるのが望ましい。 The cationic monomer forming the cationic latex polymer of the present invention preferably forms a copolymer with a non-cationic monomer in order to adjust water solubility. Examples of such non-cationic monomers include esters of acrylic acid and methacrylic acid, styrene, alkylene, ether, vinyl acetate, acrylonitrile, and the like. The cationic latex polymer of the present invention is preferably crosslinked with a monomer having two or more functional groups, such as divinylbenzene or dimethacrylate, and is preferably produced by emulsion polymerization.
前記共重合体を形成する場合に、本発明のカチ
オン性ラテツクス重合体中、カチオン性モノマー
は５〜95重量％含まれるのが好ましく、更に好ま
しくは25〜65重量％の範囲で含まれる。また非カ
チオン性モノマーは本発明のカチオン性ラテツク
ス重合体中に、５〜95重量％を含有することが好
ましく、そのうち、架橋性モノマーは0.1〜８重
量％含まれることが好ましい。 When forming the copolymer, the cationic latex polymer of the present invention preferably contains the cationic monomer in an amount of 5 to 95% by weight, more preferably 25 to 65% by weight. Further, the cationic latex polymer of the present invention preferably contains 5 to 95% by weight of the non-cationic monomer, and preferably 0.1 to 8% by weight of the crosslinking monomer.
本発明のカチオン性ラテツクス重合体の合成例
としては、特開昭51―73440号公報の実施例に記
載されているごとく、ビニルベンジルクロリドを
他のモノマーと乳化重合し、その後、第３アミン
で４級化する技術が知られている。 As an example of synthesis of the cationic latex polymer of the present invention, vinylbenzyl chloride is emulsion polymerized with other monomers, and then treated with a tertiary amine, as described in the examples of JP-A-51-73440. Techniques for quaternizing are known.
特に、好ましい本発明のカチオン性ラテツクス
重合体は、乳化重合によつて得られた第３アミン
を有するラテツクス重合体を４級化剤で４級化す
ることにより製造されたラテツクス重合体であ
る。この合成例としては特開昭55―22766号公報
に記載の技術がある。 A particularly preferred cationic latex polymer of the present invention is a latex polymer produced by quaternizing a latex polymer having a tertiary amine obtained by emulsion polymerization with a quaternizing agent. An example of this synthesis is the technique described in JP-A-55-22766.
また、別の特に好ましい４級窒素原子を有する
本発明のカチオン性ラテツクス重合体は、４級窒
素含有モノマーを親油性モノマーと乳化重合する
ことにより製造されたラテツクス重合体がある。
その合成方法は、知られている種々の方法の中か
ら選んで用いられる。その１例としては、特開昭
56―17352号公報に記載されているものがある。 Another particularly preferred cationic latex polymer of the present invention having a quaternary nitrogen atom is a latex polymer produced by emulsion polymerization of a quaternary nitrogen-containing monomer with a lipophilic monomer.
The synthesis method is selected from among various known methods. One example is the
Some are described in Publication No. 56-17352.
本発明に係る感光性樹脂組成物を塗設して成る
感光層は、露光部ではジアゾ樹脂とカチオンの反
応により硬化し、親水性を失ない、撥水性とな
る。 The photosensitive layer coated with the photosensitive resin composition according to the present invention is cured in exposed areas by the reaction between the diazo resin and cations, and becomes water repellent without losing its hydrophilicity.
しかし、ラテツクス粒子内部にカチオンが多く
存在すると、露光後も粒子内にカチオンが残留し
て、親水性が保持され、水系現像液の浸透を防ぎ
きれず、また、現像時に膨潤がおこりやすくな
り、皮膜強度を低下させる原因になる。 However, if there are a lot of cations inside the latex particles, the cations will remain inside the particles even after exposure, maintaining hydrophilicity, making it impossible to prevent the penetration of aqueous developers, and making it easier for swelling to occur during development. This may cause a decrease in film strength.
このようなことから、本発明に係る感光性樹脂
組成物におけるカチオン性ラテツクス重合体は、
ラテツクス粒子表面にカチオンをより多く配向す
るような合成法により製造されたものが特に望ま
しい。製造方法としては、先に第３アミンを有す
るラテツクス重合体を乳化重合によつて合成し、
その後に４級化剤より４級化する方法が最も適し
ている。 For this reason, the cationic latex polymer in the photosensitive resin composition according to the present invention is
Particularly desirable are those produced by a synthetic method that orients more cations on the surface of latex particles. As a manufacturing method, a latex polymer having a tertiary amine is first synthesized by emulsion polymerization,
The most suitable method is to subsequently perform quaternization using a quaternizing agent.
また、別の有用な本発明のカチオン性ラテツク
ス重合体の合成法は、４級窒素原子含有モノマー
を適当な親油性モノマーと乳化重合することによ
り製造する方法である。この合成法は、本発明の
カチオン性ラテツクス重合体中、カチオン性モノ
マー単位が少ない比率（好ましくは５〜30重量
％）で含まれる場合に適している。 Another useful method for synthesizing the cationic latex polymer of the present invention is to emulsion polymerize a quaternary nitrogen atom-containing monomer with a suitable lipophilic monomer. This synthesis method is suitable when the cationic latex polymer of the present invention contains a small proportion of cationic monomer units (preferably 5 to 30% by weight).
本発明に係る感光性樹脂組成物から得られる感
光層の光硬化反応においては、本発明のカチオン
性ラテツクス重合体中のカチオン基が重要な働き
をしている。この反応機構については明らかでな
いが、有用なカチオン基を有する本発明のカチオ
ン性ラテツクス重合体は、上述の如く４級窒素原
子を有するものの中から選ばれる。 In the photocuring reaction of the photosensitive layer obtained from the photosensitive resin composition of the present invention, the cationic groups in the cationic latex polymer of the present invention play an important role. Although the reaction mechanism is not clear, the cationic latex polymers of the present invention having useful cationic groups are selected from those having quaternary nitrogen atoms as described above.
本発明のカチオン性ラテツクス重合体の具体例
としては、下記に示す化合物があげられる。（カ
ツコ内はモル比の具体例を示す。）。 Specific examples of the cationic latex polymer of the present invention include the compounds shown below. (The numbers in brackets show specific examples of molar ratios.)
本発明に係る感光性樹脂組成物に用いられる液
状の親油性水不溶性ポリマー（以下、本発明のポ
リマーという。）は、それが液状であることが、
水現像を容易とするものである。それらが液状で
なく、固型である場合は、水現像は行なわれにく
く、水現像ができたとしても画質の悪いものとな
る。本発明の感光性樹脂組成物を水現像可能とし
ているのは、該組成物が有する適度の親水性の本
発明のカチオン性ラテツクス重合体と上記本発明
のポリマーの組み合わせによる効果が大きい。ま
た、インク着肉性に関してはインク受容部である
画線部となる感光層が親油性であることが重要な
性質となつている。上記本発明のポリマーの代わ
りに、ゼラチンやポリビニルアルコールのような
水溶性ポリマーを用いると、水現像可能だが、で
きた皮膜はインク着肉性に対しては不充分な性能
しか示さない。このため、実際には平版印刷版と
して用いるには不適当である。 The liquid lipophilic water-insoluble polymer (hereinafter referred to as the polymer of the present invention) used in the photosensitive resin composition of the present invention has the following characteristics:
It facilitates water development. If they are solid rather than liquid, it is difficult to develop them with water, and even if they can be developed with water, the image quality will be poor. The water developability of the photosensitive resin composition of the present invention is largely due to the combination of the moderately hydrophilic cationic latex polymer of the present invention possessed by the composition and the above polymer of the present invention. In addition, with respect to ink receptivity, it is an important property that the photosensitive layer, which serves as the image area, which is the ink receiving area, is lipophilic. If a water-soluble polymer such as gelatin or polyvinyl alcohol is used in place of the polymer of the present invention, water developability is possible, but the resulting film exhibits insufficient ink receptivity. Therefore, it is actually unsuitable for use as a lithographic printing plate.
本発明のポリマーは必ずしも室温で液状でなく
てもよく、本発明に係る感光性樹脂組成物の塗設
によつて得られる画像形成材料の現像処理に用い
る現像水温度の範囲で液状であればよい。この現
像は10℃〜50℃の範囲で行なうことが好ましく、
上記本発明のポリマーは融点が10℃〜50℃の範囲
であり、その温度範囲で液状であれば実質的に本
発明の目的を達成できる性能を発揮できる。ここ
で言う液状とは、流動度特性を有するものであ
り、また、融点の測定法は、ゴールドン・エム・
クライン版、インターサイエンス出版社、ニユー
ヨーク著作「ポリマーの分析化学」に記載されて
いる。 The polymer of the present invention does not necessarily have to be liquid at room temperature, but as long as it is liquid within the temperature range of the developing water used for developing the image forming material obtained by applying the photosensitive resin composition of the present invention. good. This development is preferably carried out at a temperature of 10°C to 50°C.
The above-mentioned polymer of the present invention has a melting point in the range of 10°C to 50°C, and if it is liquid in that temperature range, it can exhibit the performance that can substantially achieve the object of the present invention. The liquid mentioned here has fluidity characteristics, and the method for measuring the melting point is the Goldman M.
Described in "Analytical Chemistry of Polymers", published by Klein, Interscience Publishing, New York.
本発明に用いられるポリマーの親油性は水との
接触角が45゜以上であることが好ましく、同じく
水不溶性は20℃の純水に対する溶解度が0.1％以
下であることが好ましい。 The lipophilicity of the polymer used in the present invention is preferably such that the contact angle with water is 45° or more, and the water insolubility is preferably such that the solubility in pure water at 20°C is 0.1% or less.
本発明のポリマーは画像形成材料の感光層とさ
れたのち露光、現像処理された後も分子量が増大
することなく、元の分子量を保つているものであ
る。すなわち、非重合性であり、その性質は変化
しないものである。具体的には次のような化合物
をあげることができる。例えば、ポリエチレン、
ポリプロピレン、ポリイソプレン、ポリブタジエ
ン、ポリペンタジエン、ポリクロロプレン、ポリ
サルフアイド、ポリイソブチレン、ポリスチレ
ン、ポリメタクリル酸エステル、ポリアクリル酸
エステル、ポリ酢酸ビニル、ポリアクリロニトリ
ル等があり、比較的分子量の低いものが好まし
い。好ましい分子量はポリマーの種類によつて異
なるが、およそ数百〜数万の範囲である。 The polymer of the present invention maintains its original molecular weight without increasing its molecular weight even after being used as a photosensitive layer of an image forming material, exposed to light, and developed. That is, it is non-polymerizable and its properties do not change. Specifically, the following compounds can be mentioned. For example, polyethylene,
Examples include polypropylene, polyisoprene, polybutadiene, polypentadiene, polychloroprene, polysulfide, polyisobutylene, polystyrene, polymethacrylate, polyacrylate, polyvinyl acetate, polyacrylonitrile, etc., and those with a relatively low molecular weight are preferred. The preferred molecular weight varies depending on the type of polymer, but is in the range of approximately several hundred to several tens of thousands.
本発明に係る感光性樹脂組成物の好ましい組成
物の範囲としては、感光性ジアゾ樹脂化合物３〜
30重量％、本発明のカチオン性ラテツクス重合体
25〜90重量％、本発明のポリマー５〜70重量％で
ある。 The preferred composition range of the photosensitive resin composition according to the present invention includes photosensitive diazo resin compounds 3 to 3.
30% by weight of the cationic latex polymer of the invention
25 to 90% by weight, and 5 to 70% by weight of the polymer of the invention.
また、本発明のカチオン性ラテツクス重合体の
粒径は、10mμ〜200mμが好ましく、10mμよりも
小さいと、調製困難であり実用的ではない。一
方、その粒径が200mμよりも大きいと、最終的に
得られる画像の解像力が悪くなり、微細な網点を
再現することができなくなる。 Further, the particle size of the cationic latex polymer of the present invention is preferably 10 mμ to 200 mμ, and if it is smaller than 10 mμ, it is difficult to prepare and is not practical. On the other hand, if the particle size is larger than 200 mμ, the resolution of the final image will be poor, making it impossible to reproduce fine halftone dots.
本発明に係る感光性樹脂組成物による感光層の
塗布量は、0.1ｇ／m2〜20ｇ／m2の範囲がよく、
より好ましくは0.5ｇ／m2〜５ｇ／m2であり、こ
れより薄すぎると感光層の皮膜強度が不足し、こ
れより厚すぎると感度低下や解像力不足を生じや
すい。 The coating amount of the photosensitive layer using the photosensitive resin composition according to the present invention is preferably in the range of 0.1 g/m 2 to 20 g/m 2 .
More preferably, it is 0.5 g/m 2 to 5 g/m 2 . If it is too thin, the film strength of the photosensitive layer is insufficient, and if it is too thick, it tends to cause a decrease in sensitivity or insufficient resolution.
本発明に係る感光性樹脂組成物による感光層の
保存安定性を、よりよくするために、本発明に係
る組成物に酸性の保存剤が加えられてもよい。保
存剤としては、リン酸、クエン酸、ｐ―トルエン
スルホン酸、メタンスルホン酸、ベンゼンスルホ
ン酸、及びこの置換誘導体等がある。 In order to improve the storage stability of the photosensitive layer formed by the photosensitive resin composition according to the present invention, an acidic preservative may be added to the composition according to the present invention. Preservatives include phosphoric acid, citric acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, and substituted derivatives thereof.
本発明に係る感光性樹脂組成物を塗布して感光
層を得るのに使用される支持体としては、アルミ
ニウム、鉄、銅、それらの合金等の金属板、紙支
持体、とくに合成紙（ポリプロピレン、ポリエチ
レンラミネート紙等）、プラスチツク支持体（と
くに例えば酢酸セルロース、ポリエチレンテレフ
タレート、ポリプロピレン、ポリスチレン、塩化
ビニリデン等）を挙げることができる。かかる支
持体は、接着性改良等の目的で、電気的・化学
的・機械的に表面処理されていることが望まし
い。また下引層を有してもよい。更に又、カー
ル、表面滑りコントロールのために感光層と反対
側の面にカール防止層やマツト層を加工しても良
い。 Supports used to obtain a photosensitive layer by coating the photosensitive resin composition of the present invention include metal plates such as aluminum, iron, copper, and alloys thereof, paper supports, and especially synthetic paper (polypropylene , polyethylene laminate paper, etc.), plastic supports (in particular cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene, vinylidene chloride, etc.). Such a support is preferably surface-treated electrically, chemically, or mechanically for the purpose of improving adhesion or the like. It may also have a subbing layer. Furthermore, in order to control curling and surface slippage, an anti-curling layer or a matte layer may be formed on the surface opposite to the photosensitive layer.
本発明に係る感光性樹脂組成物を用いて画像形
成材料を製造するには、代表的には回転塗布法、
ブラシ塗布法、ドクターブレード塗布法あるいは
ホツパー塗布法等の手段を用いて塗布し乾燥す
る。塗布溶剤としては、水、アセトン、メタノー
ル、エタノール、メチルセロソルブ、エチルセロ
ソルブ、ハロゲン化炭化水素、酢酸エチル等を用
い、これらの溶液として塗布するのが一般的であ
る。また、画像形成材料の表面物性コントロール
のために、現像水可溶性又は浸透性の保護層やマ
ツト層を設けても良い。更に、本発明に係る感光
性樹脂組成物には、本発明の効果を損なわない範
囲で種々の添加剤を加えることができる。 To produce an image forming material using the photosensitive resin composition according to the present invention, typically a spin coating method,
It is applied using a brush coating method, a doctor blade coating method, a hopper coating method, or the like, and then dried. As a coating solvent, water, acetone, methanol, ethanol, methyl cellosolve, ethyl cellosolve, halogenated hydrocarbon, ethyl acetate, etc. are used, and the coating is generally carried out as a solution. Further, in order to control the surface properties of the image forming material, a developing water soluble or permeable protective layer or matte layer may be provided. Furthermore, various additives can be added to the photosensitive resin composition according to the present invention as long as they do not impair the effects of the present invention.
上記のようにしてつくられた画像形成材料は、
まず活性光線により像様露光される。ここに活性
光線としてはジアゾ樹脂化合物が感光するもので
あればどのような形式のものでも用いることがで
きる。特に好ましいのはジアゾ樹脂化合物が主と
して感光する紫外線に富む光源、例えば水銀灯や
キセノン灯である。像様露光は原稿フイルムとの
密着露光が一般的である。露光後の画像形成材料
は、適当な水系現像剤に浸漬して現像する。また
この際、スポンジ等の適当な材料を用いて材料表
面を擦接することにより現像をより効果的に行う
ことができる。擦接の強さや現像時間は、用いる
材料と現像溶媒の性質によつて適当に選ばれる。
また、現像液の温度によつてもこれらの条件をコ
ントロールできる。そして、本発明の現像溶媒は
水が公害上、労働環境・衛生上から最も好ましい
が、炭酸ナトリウムのような弱いアルカリや浸透
性をコントロールするための活性剤を添加しても
良い。 The image forming material produced as described above is
First, it is imagewise exposed to actinic light. Any type of active light can be used as long as the diazo resin compound is sensitive to the light. Particularly preferred are light sources rich in ultraviolet light to which the diazo resin compound is primarily sensitive, such as mercury lamps and xenon lamps. Imagewise exposure is generally carried out in close contact with the original film. The image-forming material after exposure is developed by immersing it in a suitable aqueous developer. Further, at this time, development can be carried out more effectively by rubbing the surface of the material using a suitable material such as a sponge. The strength of rubbing and the development time are appropriately selected depending on the materials used and the properties of the developing solvent.
These conditions can also be controlled by the temperature of the developer. As the developing solvent of the present invention, water is most preferable from the viewpoint of pollution, working environment, and hygiene, but a weak alkali such as sodium carbonate or an activator for controlling permeability may be added.
本発明に係る感光性樹脂組成物から得られる画
像形成材料は、平版印刷原稿用として他に、反射
型支持体（例えば、白色不透明支持体）を用いて
校正用とすること、又、プリント配線基版用のレ
ジスト等としても用いられる。 The image forming material obtained from the photosensitive resin composition according to the present invention can be used not only for lithographic printing manuscripts, but also for proofing using a reflective support (for example, a white opaque support), and for printed wiring. It is also used as a resist for the base plate.
以下、実施例を挙げて本発明を例証するが、本
発明の実施態様はこれらに限定されない。なお、
以下の実施例において「部」とは、とくに断わり
のない限り「重量部」を示す。 The present invention will be illustrated below with reference to examples, but the embodiments of the present invention are not limited thereto. In addition,
In the following examples, "parts" refer to "parts by weight" unless otherwise specified.
実施例 １
厚さ0.3mmのアルミニウム版を20％リン酸ソー
ダ水溶液に浸漬して脱脂し、電解研磨を行なつた
後、硫酸中で陽極酸化し、更にメタケイ酸ソーダ
水溶液にて処理し、水洗乾燥を行なつた。Example 1 An aluminum plate with a thickness of 0.3 mm was immersed in a 20% sodium phosphate aqueous solution to degrease it, electrolytically polished, anodized in sulfuric acid, further treated with a sodium metasilicate aqueous solution, and washed with water. I did drying.
この基板（支持体）に、下記組成の感光液で乾
燥後の膜厚が3.0μｍになるように被覆して試料を
得た。 This substrate (support) was coated with a photosensitive solution having the following composition so that the film thickness after drying was 3.0 μm to obtain a sample.
〔前記例示化合物（11）のラテツクス重合体
固型分10％のメチルセロソルブ分散液 40部
ジアゾ樹脂（ジフエニルアミン―ｐ―ジアゾ
ニウム塩とホルムアルデヒドの縮合物とヘキ
サフルオロリン酸アンモニウムとの反応生成
物）10％メチルセロソルブ溶液 20部
液状ポリブタジエン（日本曹達(株)社製
NISSO―PB1000）10％メチルエチルケトン
溶液 40部〕
上記試料上にネガフイルム、コダツクステツプ
タブレツトNo.２を密着させアイドルフイン2000
〔岩崎電気(株)社製，2KWメタルハライドランプ〕
で30秒間露光し、25℃の水中で１分間スポンジで
擦すり末露光部分を除去して印刷版を得た。ステ
ツプタブレツトの硬化段数は６段であつた。次
に、この印刷版を枚葉オフセツト印刷機にかけて
上質紙に印刷したところ、４万枚以上の良好な印
刷物が得られた。[Methyl cellosolve dispersion of latex polymer solids content of 10% of the above-mentioned exemplary compound (11) 40 parts Diazo resin (reaction product of diphenylamine-p-diazonium salt, formaldehyde condensate, and ammonium hexafluorophosphate) 10 % methyl cellosolve solution 20 parts Liquid polybutadiene (manufactured by Nippon Soda Co., Ltd.)
NISSO-PB1000) 10% methyl ethyl ketone solution 40 parts] Apply negative film and Kodak Step Tablet No. 2 on the above sample and use Idol Fin 2000.
[2KW metal halide lamp manufactured by Iwasaki Electric Co., Ltd.]
The plate was exposed to light for 30 seconds, and the exposed portion was removed by rubbing with a sponge in water at 25°C for 1 minute to obtain a printing plate. The number of curing stages of the step tablet was six. Next, when this printing plate was printed on high-quality paper using a sheet-fed offset printing machine, more than 40,000 good-quality prints were obtained.
実施 ２
実施例１と同様の処理をしたアルミニウム版
に、下記組成の感光液で乾燥後の皮膜が3.0μにな
るように被覆した。Implementation 2 An aluminum plate treated in the same manner as in Example 1 was coated with a photosensitive solution having the following composition so that the film after drying had a thickness of 3.0μ.
〔前記例示化合物（11）のラテツクス重合体
固型分10％のメタノール分散液 50部
ジアゾ樹脂（実施例１で用いたのと同じジア
ゾ樹脂）10％メチルセロソルブ溶液 20部
液状ポリスチレン（三洋化成工業(株)社製）10
％メチルセロソルブ溶液 30部〕
上記試料を実施例１と同様に露光、現像し、印
刷版を得た。この印刷版を枚葉オフセツト印刷機
にかけて上質紙に印刷したところ、良質な印刷物
が２万枚以上得られた。[Methanol dispersion of 10% latex polymer solids of the above-mentioned exemplified compound (11) 50 parts diazo resin (same diazo resin used in Example 1) 10% methyl cellosolve solution 20 parts liquid polystyrene (Sanyo Chemical Co., Ltd.) Co., Ltd.) 10
% methyl cellosolve solution 30 parts] The above sample was exposed and developed in the same manner as in Example 1 to obtain a printing plate. When this printing plate was printed on high-quality paper using a sheet-fed offset printing machine, more than 20,000 high-quality prints were obtained.
実施例 ３
上記実施例１および２で得られた印刷版の各試
料を40℃，80％RHの雰囲気中に２日間保存した
後、実施例１と同様に露光、現像したところ、ス
テツプタブレツトの硬化段数は６段であつて、保
存による感度（硬化段数）の変動が小さいことを
確認した。Example 3 Each sample of the printing plate obtained in Examples 1 and 2 above was stored in an atmosphere of 40°C and 80% RH for 2 days, and then exposed and developed in the same manner as in Example 1. The number of curing stages was six, and it was confirmed that the sensitivity (the number of curing stages) varied little due to storage.
Claims (1)
するカチオン性ラテツクス重合体、および液状の
親油性水不溶性ポリマーを含み、露光域において
前記感光性ジアゾ樹脂化合物と前記カチオンの反
応により硬化し、親水性を失い、撥水性となるこ
とを特徴とする感光性樹脂組成物。1 Contains a photosensitive diazo resin compound, a cationic latex polymer having a quaternary nitrogen atom, and a liquid lipophilic water-insoluble polymer, which is cured by the reaction between the photosensitive diazo resin compound and the cation in the exposed region, and becomes hydrophilic. A photosensitive resin composition characterized in that it loses water and becomes water repellent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11986882A JPH0247738B2 (en) | 1982-07-12 | 1982-07-12 | KANKOSEIJUSHISOSEIBUTSU |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11986882A JPH0247738B2 (en) | 1982-07-12 | 1982-07-12 | KANKOSEIJUSHISOSEIBUTSU |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5910946A JPS5910946A (en) | 1984-01-20 |
| JPH0247738B2 true JPH0247738B2 (en) | 1990-10-22 |
Family
ID=14772248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11986882A Expired - Lifetime JPH0247738B2 (en) | 1982-07-12 | 1982-07-12 | KANKOSEIJUSHISOSEIBUTSU |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0247738B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05127372A (en) * | 1991-11-01 | 1993-05-25 | Nippon Paint Co Ltd | Photosensitive resin for lithographic printing and resin composition |
-
1982
- 1982-07-12 JP JP11986882A patent/JPH0247738B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5910946A (en) | 1984-01-20 |
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