JPH04323657A - Color proofing method for color printed original - Google Patents
Color proofing method for color printed originalInfo
- Publication number
- JPH04323657A JPH04323657A JP9208291A JP9208291A JPH04323657A JP H04323657 A JPH04323657 A JP H04323657A JP 9208291 A JP9208291 A JP 9208291A JP 9208291 A JP9208291 A JP 9208291A JP H04323657 A JPH04323657 A JP H04323657A
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive
- color
- recording material
- electron
- thermosensitive recording
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N cinnamyl alcohol Chemical compound OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 125000005520 diaryliodonium group Chemical group 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- POSWICCRDBKBMH-UHFFFAOYSA-N dihydroisophorone Natural products CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- MLSGRWDEDYJNER-UHFFFAOYSA-N ethyl 2-anilinoacetate Chemical compound CCOC(=O)CNC1=CC=CC=C1 MLSGRWDEDYJNER-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- CPBQJMYROZQQJC-UHFFFAOYSA-N helium neon Chemical compound [He].[Ne] CPBQJMYROZQQJC-UHFFFAOYSA-N 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical class [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- CFKPIIMZDNLAQL-UHFFFAOYSA-N methyl acetate;toluene Chemical compound COC(C)=O.CC1=CC=CC=C1 CFKPIIMZDNLAQL-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- JZBZLRKFJWQZHU-UHFFFAOYSA-N n,n,2,4,6-pentamethylaniline Chemical compound CN(C)C1=C(C)C=C(C)C=C1C JZBZLRKFJWQZHU-UHFFFAOYSA-N 0.000 description 1
- ALXIOUGHHXXLKX-UHFFFAOYSA-N n,n-dimethyl-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C)C ALXIOUGHHXXLKX-UHFFFAOYSA-N 0.000 description 1
- VHRFGJFNYHVDFB-UHFFFAOYSA-N n-ethyl-1-hydroxy-2-phenylethenesulfonamide Chemical compound CCNS(=O)(=O)C(O)=CC1=CC=CC=C1 VHRFGJFNYHVDFB-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 125000005506 phthalide group Chemical group 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 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
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 150000004654 triazenes Chemical class 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 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
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、カラー印刷用原稿の色
校正方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for color proofing originals for color printing.
【0002】0002
【従来の技術】カラープルーフの代表的な方式の一つと
して、オーバーレイ方式がある。この方式は、各色の画
像を有するフィルムを重ね合わせて多色画像を再現させ
る方式で、各色の色原稿を個別に正確に校正できるとい
う特徴を持っている。このオーバーレイ方式に用いる記
録材料として様々な記録材料が知られているが各々欠点
を有している。代表的なオーバーレイ方式としてジアゾ
ニウム化合物を塗設した記録材料を露光後アンモニア現
像する方式が知られているが、この方式の場合、アンモ
ニアの臭いがする、アンモニア現像液の交換の手間が要
る等の欠点がある。また、他の方式として、顔料を練り
込んだフォトポリマー層を塗設した記録材料を用い、露
光後に非硬化部分を溶剤もしくはアルカリ水もしくは水
現像で洗い流す方式が知られているが、やはり現像液の
管理が必要で改善が求められている。2. Description of the Related Art One of the typical methods of color proofing is an overlay method. This method reproduces a multicolor image by overlapping films containing images of each color, and has the feature that each color original can be accurately proofread individually. Various recording materials are known as recording materials used in this overlay method, but each has its own drawbacks. As a typical overlay method, a method is known in which a recording material coated with a diazonium compound is developed with ammonia after exposure. However, in this method, there is an odor of ammonia, and it is time-consuming to replace the ammonia developer. There are drawbacks. Another known method is to use a recording material coated with a photopolymer layer mixed with pigment, and after exposure, wash off the uncured areas with a solvent, alkaline water, or water development. management is necessary and improvements are required.
【0003】0003
【発明が解決しようとする課題】本発明の目的は、画像
露光・熱現像という簡便な操作だけでカラー印刷原稿を
校正する方法を提供することにある。更には、現像液や
アンモニアやトナー等の現像剤が不要で、作業環境を汚
す心配の無い校正方法を提供することにある。更には、
高解像度・高画質の記録材料を用いた高精度の校正を行
う方法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for proofreading a color printed original using simple operations such as image exposure and thermal development. Furthermore, it is an object of the present invention to provide a calibration method that does not require a developing solution or a developer such as ammonia or toner, and does not contaminate the working environment. Furthermore,
The object of the present invention is to provide a method for performing highly accurate calibration using recording materials with high resolution and high image quality.
【0004】0004
【課題を解決するための手段】本発明の目的は、ポジの
カラー印刷原稿と対応する色に発色させた感光・感熱性
記録材料を複数枚重ねてカラー印刷原稿の色校正を行う
方法に於いて、該感光・感熱性記録材料が、露光により
光硬化性組成物の露光部分が光硬化した潜像が形成され
、加熱により未硬化部分の重合性の電子受容性化合物が
その潜像に応じてマイクロカプセル外からマイクロカプ
セル中に移動してマイクロカプセル中の電子供与性無色
染料を発色させて色画像を形成する感光・感熱層を透明
支持体上に設けた感光・感熱性記録材料である事を特徴
とするカラー印刷原稿の色校正方法、もしくは、ネガの
カラー印刷原稿と対応する色に発色させた感光・感熱性
記録材料を複数枚重ねてカラー印刷原稿の色校正を行う
方法に於いて、該感光・感熱性記録材料が露光により光
硬化性組成物の露光部分が光硬化した潜像が形成され、
加熱により未硬化部分の重合性でかつ消色性化合物がそ
の潜像に応じてマイクロカプセル外からマイクロカプセ
ル中に移動してマイクロカプセル中の電子供与性無色染
料発色体を消色させて画像を形成する感光・感熱層を透
明支持体上に設けた感光・感熱性記録材料である事を特
徴とするカラー印刷原稿の色校正方法を用いる事で達成
された。[Means for Solving the Problems] An object of the present invention is to provide a method for color proofing a color printed document by stacking a plurality of photosensitive/thermosensitive recording materials colored in colors corresponding to a positive color printed document. When the photosensitive/thermosensitive recording material is exposed to light, a latent image is formed in which the exposed portion of the photocurable composition is photocured, and upon heating, the polymerizable electron-accepting compound in the uncured portion responds to the latent image. This is a photosensitive/thermosensitive recording material provided with a photosensitive/thermosensitive layer on a transparent support, which moves from outside the microcapsules into the microcapsules and develops color with the electron-donating colorless dye in the microcapsules to form a color image. A method for color proofing a color printed original, characterized by the The photosensitive/thermosensitive recording material is exposed to light to form a latent image in which the exposed portions of the photocurable composition are photocured,
By heating, the polymerizable and decolorizable compound in the uncured portion moves from outside the microcapsule into the microcapsule according to its latent image, decoloring the electron-donating colorless dye coloring material in the microcapsule, and creating an image. This was achieved by using a color proofing method for color printing originals, which is characterized in that the photosensitive/thermosensitive layer to be formed is a photosensitive/thermosensitive recording material provided on a transparent support.
【0005】この本発明に好ましく使用できる感光・感
熱性記録材料の例としては、例えば、特開平3ー723
58号もしくは欧州公開特許第0412570A2号の
記述を参考にできる。以下に本発明に好ましく使用でき
る記録材料の代表的な例を挙げて説明する。Examples of photosensitive/thermosensitive recording materials that can be preferably used in the present invention include those disclosed in Japanese Patent Application Laid-Open No. 3-723.
58 or European Patent Publication No. 0412570A2 can be referred to. Typical examples of recording materials that can be preferably used in the present invention will be described below.
【0006】ポジ型の記録材料の具体的な例としては、
例えば、マイクロカプセル外に電子受容性部と重合性の
ビニルモノマー部を同一分子内に有する化合物と光重合
開始剤を含有する光重合性組成物と電子供与性の無色染
料を内包するマイクロカプセルとを含有する層を塗設し
た記録材料を挙げることができる。この記録材料を露光
するとマイクロカプセル外にある光重合性組成物の露光
された部位が重合して潛像が形成され、その後、加熱す
ると電子受容性化合物がその潛像に応じて感材内で移動
してマイクロカプセル内の電子供与性の無色染料を発色
させ良好なコントラストのポジ色画像を形成することが
できる。ネガ型の記録材料の具体的な例としては、マイ
クロカプセル外に電子受容性化合物と重合性でかつ電子
供与性無色染料の発色体を消色する能力のあるビニルモ
ノマーと光重合開始剤を含有する光重合性組成物と電子
供与性の無色染料を内包するマイクロカプセルとを含有
する層を塗設した記録材料を挙げることができる。この
記録材料を露光するとマイクロカプセル外にある光重合
性組成物の露光された部位が重合して潛像が形成され、
その後、加熱すると全体が均一に発色すると同時に未重
合部の消色性モノマーがマイクロカプセル内移動して電
子供与性無色染料発色体を消色させ、良好なコントラス
トのネガ画像を形成することができる。Specific examples of positive recording materials include:
For example, a photopolymerizable composition containing a photopolymerization initiator and a compound having an electron-accepting moiety and a polymerizable vinyl monomer moiety in the same molecule outside the microcapsule, and a microcapsule containing an electron-donating colorless dye. Examples include recording materials coated with a layer containing . When this recording material is exposed to light, the exposed portion of the photopolymerizable composition outside the microcapsules polymerizes to form a latent image, and then, when heated, the electron-accepting compound is absorbed within the sensitive material according to the latent image. The electron-donating colorless dye inside the microcapsules can be moved to develop color, and a positive color image with good contrast can be formed. A specific example of a negative recording material is a microcapsule containing an electron-accepting compound, a vinyl monomer that is polymerizable, and has the ability to erase the color former of an electron-donating colorless dye, and a photopolymerization initiator. Examples include recording materials coated with a layer containing a photopolymerizable composition and microcapsules containing an electron-donating colorless dye. When this recording material is exposed to light, the exposed portion of the photopolymerizable composition outside the microcapsules is polymerized to form a latent image.
Thereafter, when heated, the entire color develops uniformly, and at the same time, the unpolymerized part of the color erasing monomer moves into the microcapsules, erasing the electron-donating colorless dye coloring body, forming a negative image with good contrast. .
【0007】本発明の感光・感熱性記録材料を更に詳細
に説明すると、本発明に用いる主にポジ型記録材料で用
いられる電子受容性でかつ重合性のビニルモノマーとし
ては分子中に電子受容性基とビニル基とを含有する化合
物であればよい。このような化合物としては、例えば特
開昭63−173682号に記載されているヒドロキシ
基を有する安息香酸のメタアクリロキシエチルエステル
や同様の合成法で合成できるアクリロキシエチルエステ
ルや同59−83693号、同60−141587号、
同62−99190号に記載されているヒドロキシ基を
有する安息香酸とヒドロキシメチルスチレンとのエステ
ルや欧州特許29323号に記載されているヒドロキシ
スチレンや特開昭62−167077号、同62−16
708号に記載されているハロゲン化亜鉛のN−ビニル
イミダゾール錯体や同63−317558号に記載され
ている顕色剤モノマー等を参考にして合成できる様々な
化合物が使用できる。To explain the photosensitive/thermosensitive recording material of the present invention in more detail, the electron-accepting and polymerizable vinyl monomer used mainly in the positive recording material of the present invention has an electron-accepting property in the molecule. Any compound containing a group and a vinyl group may be used. Examples of such compounds include methacryloxyethyl ester of benzoic acid having a hydroxyl group as described in JP-A No. 63-173682, acryloxyethyl ester synthesized by a similar synthesis method, and JP-A No. 59-83693. , No. 60-141587,
The ester of benzoic acid having a hydroxyl group and hydroxymethylstyrene described in JP-A-62-99190, the hydroxystyrene described in European Patent No. 29323, JP-A-62-167077, JP-A-62-16
Various compounds can be used that can be synthesized with reference to the N-vinylimidazole complex of zinc halide described in No. 708 and the color developer monomer described in No. 63-317558.
【0008】具体例としては例えば、スチレンスルホニ
ルアミノサリチル酸、ビニルベンジルオキシフタル酸、
β−メタクリロキシエトキシサリチル酸亜鉛、β−アク
リロキシエトキシサリチル酸亜鉛、ビニロキシエチルオ
キシ安息香酸、β−メタクリロキシエチルオルセリネー
ト、β−アクリロキシエチルオルセリネート、β−メタ
クリロキシエトキシフェノール、β−アクリロキシエト
キシフェノール、β−メタクリロキシエチル−β−レゾ
ルシネート、β−アクリロキシエチル−β−レゾルシネ
ート、ヒドロキシスチレンスルホン酸−N−エチルアミ
ド、β−メタクリロキシプロピル−p−ヒドロキシベン
ゾエート、β−アクリロキシプロピル−p−ヒドロキシ
ベンゾエート、メタクリロキシメチルフェノール、アク
リロキシメチルフェノール、メタクリルアミドプロパン
スルホン酸、アクリルアミドプロパンスルホン酸、β−
メタクリロキシエトキシ−ジヒドロキシベンゼン、β−
アクリロキシエトキシ−ジヒドロキシベンゼン、γ−ス
チレンスルホニルオキシ−β−メタクリロキシプロパン
カルボン酸、γ−アクリロキシプロピル−α−ヒドロキ
シエチルオキシサリチル酸、β−ヒドロキシエトキシカ
ルボニルフェノール、β−メタクリロキシエチル−p−
ヒドロキシシンナメート、β−アクリロキシエチル−p
−ヒドロキシシンナメート、3,5ジスチレンスルホン
酸アミドフェノール、メタクリロキシエトキシフタル酸
、アクリロキシエトキシフタル酸、メタクリル酸、アク
リル酸、メタクリロキシエトキシヒドロキシナフトエ酸
、アクリロキシエトキシヒドロキシナフトエ酸、3−β
−ヒドロキシエトキシフェノール、β−メタクリロキシ
エチル−p−ヒドロキシベンゾエート、β−アクリロキ
シエチル−p−ヒドロキシベンゾエート、β’−メタク
リロキシエチル−β−レゾルシネート、β−メタクリロ
キシエチルオキシカルボニルヒドロキシ安息香酸、β−
アクリロキシエチルオキシカルボニルヒドロキシ安息香
酸、N,N’−ジ−β−メタクリロキシエチルアミノサ
リチル酸、N,N’−ジ−β−アクリロキシエチルアミ
ノサリチル酸、N,N’−ジ−β−メタクリロキシエチ
ルアミノスルホニルサリチル酸、N,N’−ジ−β−ア
クリロキシエチルアミノスルホニルサリチル酸などやこ
れらの金属塩例えば亜鉛塩を好ましく用いる事ができる
。Specific examples include styrenesulfonylaminosalicylic acid, vinylbenzyloxyphthalic acid,
Zinc β-Methacryloxyethoxysalicylate, Zinc β-Acryloxyethoxysalicylate, Vinyloxyethyloxybenzoic acid, β-Methacryloxyethyl orselinate, β-Acryloxyethyl orselinate, β-Methacryloxyethoxyphenol, β- Acryloxyethoxyphenol, β-methacryloxyethyl-β-resorcinate, β-acryloxyethyl-β-resorcinate, hydroxystyrenesulfonic acid-N-ethylamide, β-methacryloxypropyl-p-hydroxybenzoate, β-acryloxypropyl -p-hydroxybenzoate, methacryloxymethylphenol, acryloxymethylphenol, methacrylamidepropanesulfonic acid, acrylamidepropanesulfonic acid, β-
Methacryloxyethoxy-dihydroxybenzene, β-
Acryloxyethoxy-dihydroxybenzene, γ-styrenesulfonyloxy-β-methacryloxypropanecarboxylic acid, γ-acryloxypropyl-α-hydroxyethyloxysalicylic acid, β-hydroxyethoxycarbonylphenol, β-methacryloxyethyl-p-
Hydroxycinnamate, β-acryloxyethyl-p
-Hydroxycinnamate, 3,5 distyrene sulfonamide phenol, methacryloxyethoxyphthalic acid, acryloxyethoxyphthalic acid, methacrylic acid, acrylic acid, methacryloxyethoxyhydroxynaphthoic acid, acryloxyethoxyhydroxynaphthoic acid, 3-β
-Hydroxyethoxyphenol, β-methacryloxyethyl-p-hydroxybenzoate, β-acryloxyethyl-p-hydroxybenzoate, β'-methacryloxyethyl-β-resorcinate, β-methacryloxyethyloxycarbonylhydroxybenzoic acid, β −
Acryloxyethyloxycarbonylhydroxybenzoic acid, N,N'-di-β-methacryloxyethylaminosalicylic acid, N,N'-di-β-acryloxyethylaminosalicylic acid, N,N'-di-β-methacryloxy Ethylaminosulfonylsalicylic acid, N,N'-di-β-acryloxyethylaminosulfonylsalicylic acid, and metal salts thereof, such as zinc salts, can be preferably used.
【0009】本発明の記録材料に好適に用いられる光重
合開始剤としては、前記のビニルモノマーの光重合を開
始し得る化合物のなかから1種または2種以上の化合物
を組み合わせて選ぶことができる。光重合開始剤の好ま
しい具体例として、次の化合物を挙げることができる。
芳香族ケトン類:例えば、ベンゾフェノン、4,4’−
ビス(ジメチルアミノ)ベンゾフェノン、4−メトキシ
−4’−ジメチルアミノベンゾフェノン、4,4’−ジ
メトキシベンゾフェノン、4−ジメチルアミノベンゾフ
ェノン、4−ジメチルアミノアセトフェノン、ベンジル
、アントラキノン、2−tert−ブチルアントラキノ
ン、2−メチルアントラキノン、キサントン、チオキサ
ントン、2−クロルチオキサントン、2,4−ジエチル
チオキサントン、フルオレノン、アクリドン ; およ
びベンゾインおよびベンゾインエーテル類:例えばベン
ゾインメチルエーテル、ベンゾインエチルエーテル、ベ
ンゾインイソプロピルエーテル、ベンゾインフェニルエ
ーテル ; および2,4,5−トリアリールイミダゾ
ール二量体:例えば2−(o−クロロフェニル)−4,
5−ジフェニルイミダゾール二量体、2−(o−クロロ
フェニル)−4,5−ジ(m−メトキシフェニル)イミ
ダゾール二量体、2−(o−フルオロフェニル)−4,
5−ジフェニルイミダゾール二量体、2−(o−メトキ
シフェニル)−4,5−ジフェニルイミダゾール二量体
、2−(p−メトキシフェニル)−4,5−ジフェニル
イミダゾール二量体 ; およびポリハロゲン化合物、
例えば四臭化炭素、フェニルトリブロモメチルスルホン
、フェニルトリクロロメチルケトンおよび特開昭53−
133428号、特公昭57−1819号、特公昭57
−6096号、米国特許第3615455号の各明細書
中に記載の化合物、特開昭58−29803号記載のト
リハロゲン置換メチル基を有するS−トリアジン誘導体
:例えば、2,4,6−トリス(トリクロロメチル)−
S−トリアジン、2−メトキシ−4,6−ビス(トリク
ロロメチル)−S−トリアジン、2−アミノ−4,6−
ビス(トリクロロメチル)−S−トリアジン、2−(P
−メトキシスチリル)−4,6−ビス(トリクロロメチ
ル)−S−トリアジン等の化合物。 ; および例えば
特開昭59−189340号記載の有機過酸化物:例え
ばメチルエチルケトンパーオキサイド、シクロヘキサノ
ンパーオキサイド、3,3,5−トリメチルシクロヘキ
サノンパーオキサイド、ベンゾイルパーオキサイド、ジ
ターシャリーブチルジパーオキシイソフタレート、2,
5−ジメチル−2,5−ジ(ベンゾイルパーオキシ)ヘ
キサン、ターシャリーブチルパーオキシベンゾエート、
α,α’−ビス(ターシャリーブチルパーオキシイソプ
ロピル)ベンゼン、ジクミルパーオキサイド、3,3’
,4,4’−テトラ−(ターシャリイブチルパーオキシ
カルボニル)ベンゾフェノン等の化合物。および例えば
米国特許第4743530号に記載のアジニウム塩化合
物 ; および例えばヨーロッパ特許第0223587
号に記載の有機ホウ素化合物:例えばトリフェニールブ
チールボレートのテトラメチルアンモニウム塩、トリフ
ェニールブチールボレートのテトラブチルアンモニウム
塩、トリ(P−メトキシフェニール)ブチールボレート
のテトラメチルアンモニウム塩等;その他ジアリールヨ
ードニウム塩類や鉄アレン錯体等当業界周知の光重合開
始剤等が有用に使用できる。As the photopolymerization initiator suitably used in the recording material of the present invention, one type or a combination of two or more types of compounds can be selected from the above-mentioned compounds capable of initiating photopolymerization of vinyl monomers. . Preferred specific examples of the photopolymerization initiator include the following compounds. Aromatic ketones: for example, benzophenone, 4,4'-
Bis(dimethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2 - methylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone, acridone; and benzoin and benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether; and 2 ,4,5-triarylimidazole dimer: e.g. 2-(o-chlorophenyl)-4,
5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,
5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer; and polyhalogen compound ,
For example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, and
No. 133428, Special Publication No. 57-1819, Special Publication No. 57
-6096, U.S. Pat. No. 3,615,455, S-triazine derivatives having a trihalogen-substituted methyl group described in JP-A-58-29803: For example, 2,4,6-tris( trichloromethyl)-
S-triazine, 2-methoxy-4,6-bis(trichloromethyl)-S-triazine, 2-amino-4,6-
Bis(trichloromethyl)-S-triazine, 2-(P
Compounds such as -methoxystyryl)-4,6-bis(trichloromethyl)-S-triazine. and organic peroxides such as those described in JP-A-59-189340, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, benzoyl peroxide, ditertiary butyl diperoxy isophthalate, 2,
5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxybenzoate,
α,α'-bis(tert-butylperoxyisopropyl)benzene, dicumyl peroxide, 3,3'
, 4,4'-tetra-(tert-butylperoxycarbonyl)benzophenone and the like. and azinium salt compounds as described, for example, in US Pat. No. 4,743,530; and, for example, in European Patent No. 0,223,587.
Organoboron compounds described in the No. 2003-2013: for example, tetramethylammonium salt of triphenylbutylborate, tetrabutylammonium salt of triphenylbutylborate, tetramethylammonium salt of tri(P-methoxyphenyl)butylborate, etc.; other diaryliodonium salts Photopolymerization initiators well known in the art, such as iron allene complexes and iron allene complexes, can be usefully used.
【0010】これらの光重合開始剤の中で特に好ましい
化合物としてはベンゾインエーテル類、トリハロゲン置
換メチル基を有するS−トリアジン誘導体、有機過酸化
物、アジニウム塩化合物および有機ホウ素化合物を挙げ
ることができる。光重合開始剤の含有量は、光重合性組
成物の全重量基準で、好ましくは0.01〜20重量%
、そしてより好ましくは0.2〜15重量%であり、最
も好ましい含有量は5〜10重量%である。0.01重
量%未満では感度が不足し、10重量%を越えると感度
の増加は期待できない。Among these photopolymerization initiators, particularly preferred compounds include benzoin ethers, S-triazine derivatives having a trihalogen-substituted methyl group, organic peroxides, azinium salt compounds, and organic boron compounds. . The content of the photopolymerization initiator is preferably 0.01 to 20% by weight based on the total weight of the photopolymerizable composition.
, and more preferably from 0.2 to 15% by weight, and most preferably from 5 to 10% by weight. If it is less than 0.01% by weight, the sensitivity will be insufficient, and if it exceeds 10% by weight, no increase in sensitivity can be expected.
【0011】本発明の記録材料の光硬化性組性物には重
合性のビニルモノマーおよび光重合開始剤のほかにその
感光波長を調整するための分光増感色素を含有してもよ
い。分光増感色素としては当業界公知の様々な化合物を
使用することができる。分光増感色素の例は上述した光
重合開始剤に関する特許や、Research Dis
closure,Vol.200,1980年12月,
Item 20036や「増感剤」(徳丸克巳・大河原
信/編、講談社1987年)の160−163ページ等
を参考にできる。The photocurable composition of the recording material of the present invention may contain, in addition to the polymerizable vinyl monomer and the photopolymerization initiator, a spectral sensitizing dye for adjusting the wavelength of light to which it is sensitive. Various compounds known in the art can be used as the spectral sensitizing dye. Examples of spectral sensitizing dyes are the patents related to photopolymerization initiators mentioned above and Research Dis
closure, Vol. 200, December 1980,
Item 20036 and pages 160-163 of "Sensitizer" (edited by Katsumi Tokumaru and Shin Okawara, Kodansha 1987) can be referred to.
【0012】具体的な分光増感色素の例としては、例え
ば、特開昭58−15503号公報には3−ケトクマリ
ン化合物が、特開昭58−40302号公報にはチオピ
リリウム塩が、特公昭59−28328号、同60−5
3300号にはナフトチアゾールメロシアニン化合物が
、特公昭61−9621号、同62−3842号、特開
昭59−89303号、同60−60104号各公報に
はそれぞれメロシアニン化合物が開示されている。これ
らの分光増感剤によって光重合開始剤の分光感度は可視
域までも伸ばすことができる。上述の例では光重合開始
剤としてトリハロメチル−S−トリアジン化合物を取上
げているが他の光重合開始剤と組合せても良い。分光増
感色素としては、ケト色素であるクマリン (ケトクマ
リン又はスルホノクマリンも含まれる)色素、メロスチ
リル色素、オキソノール色素及びヘミオキソノール色素
、非ケト色素である非ケトポリメチン色素、アントラセ
ン色素、ローダミン色素、アクリジン色素、アニリン色
素及びアゾ色素、非ケトポリメチン色素としてのシアニ
ン、ヘミシアニン及びスチリル色素等が含まれる。Specific examples of spectral sensitizing dyes include 3-ketocoumarin compounds in JP-A-58-15503, thiopyrylium salts in JP-A-58-40302, and thiopyrylium salts in JP-A-58-40302. -28328, 60-5
No. 3300 discloses naphthothiazole merocyanine compounds, and Japanese Patent Publications Nos. 61-9621, 62-3842, 59-89303, and 60-60104 disclose merocyanine compounds. These spectral sensitizers can extend the spectral sensitivity of the photopolymerization initiator to the visible range. In the above example, a trihalomethyl-S-triazine compound is used as a photopolymerization initiator, but it may be combined with other photopolymerization initiators. Spectral sensitizing dyes include keto dyes such as coumarin (including ketocoumarin or sulfonocoumarin) dyes, merostyryl dyes, oxonol dyes, and hemioxonol dyes, non-keto dyes such as non-keto polymethine dyes, anthracene dyes, rhodamine dyes, Included are acridine dyes, aniline dyes and azo dyes, cyanine, hemicyanine and styryl dyes as non-keto polymethine dyes.
【0013】また、本発明の記録材料の光重合性組成物
には、更に重合を促進するための助剤として、還元剤例
えば酸素除去剤 (oxygen scavenger
)及び活性水素ドナーの連鎖移動剤、さらに連鎖移動的
に重合を促進するその他の化合物を添加することもでき
る。有用であることの見いだされている酸素除去剤はホ
スフイン、ホスホネート、ホスフアイト、第1錫塩及び
酸素により容易に酸化されるその他の化合物である。例
えばN−フエニルグリシン、トリメチルバルビツール酸
、N,N−ジメチル−2,6−ジイソプロピルアニリン
、N,N,N−2,4,6−ペンタメチルアニリン等で
ある。さらに以下に示すようなチオール類、チオケトン
類、トリハロメチル化合物、ロフインダイマー化合物、
ヨードニウム塩類、スルホニウム塩類、アジニウム塩類
、有機過酸化物等も重合促進剤として有用である。The photopolymerizable composition of the recording material of the present invention may further contain a reducing agent, such as an oxygen scavenger, as an auxiliary agent for promoting polymerization.
) and a chain transfer agent for an active hydrogen donor, as well as other compounds that promote polymerization in a chain transfer manner. Oxygen scavengers that have been found to be useful are phosphines, phosphonates, phosphites, stannous salts and other compounds that are readily oxidized by oxygen. Examples include N-phenylglycine, trimethylbarbituric acid, N,N-dimethyl-2,6-diisopropylaniline, and N,N,N-2,4,6-pentamethylaniline. Furthermore, thiols, thioketones, trihalomethyl compounds, lofin dimer compounds as shown below,
Iodonium salts, sulfonium salts, azinium salts, organic peroxides, and the like are also useful as polymerization accelerators.
【0014】また、本発明に用いるネガの記録材料の光
重合性組成物には電子受容性化合物を用いることが好ま
しい。また、ポジの記録材料中の光硬化性組成物中には
必要に応じてこの電子受容性化合物を添加することがで
き、この添加により発色濃度が向上する。電子受容性化
合物としてはとしては、フエノ−ル誘導体、サリチル酸
誘導体、芳香属カルボン酸の金属塩、酸性白土、ベント
ナイト、ノボラック樹脂、金属処理ノボラック樹脂、金
属錯体などが挙げられる。これらの例は特公昭40−9
309号、特公昭45−14039号、特開昭52−1
40483号、特開昭48−51510号、特開昭57
−210886号、特開昭58−87089号、特開昭
59−11286号、特開昭60−176795号、特
開昭61−95988号等に記載されている。これらの
電子受容性化合物を併用する場合は電子供与性無色染料
の5〜1000 重量%使用することが好ましい。Further, it is preferable to use an electron-accepting compound in the photopolymerizable composition of the negative recording material used in the present invention. Further, this electron-accepting compound can be added to the photocurable composition in the positive recording material as needed, and the color density is improved by this addition. Examples of the electron-accepting compound include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins, and metal complexes. Examples of these are
No. 309, JP 45-14039, JP 52-1
No. 40483, JP-A-48-51510, JP-A-57
JP-A-210886, JP-A-58-87089, JP-A-59-11286, JP-A-60-176795, JP-A-61-95988, and the like. When these electron-accepting compounds are used in combination, it is preferable to use them in an amount of 5 to 1000% by weight of the electron-donating colorless dye.
【0015】本発明に用いるネガ記録材料の光硬化性組
性物には重合性でかつ消色性の化合物としては分子内に
少なくとも1個のビニル基を有し、かつ、電子供与性無
色染料と電子受容性化合物との発色した複合体を消色す
る化合物をさす。それらの化合物の代表例としては例え
ばアクリル酸及びその塩、アクリル酸エステル類、アク
リルアミド類;メタクリル酸及びその塩、メタクリル酸
エステル類、メタクリルアミド類;無水マレイン酸、マ
レイン酸エステル類;イタコン酸、イタコン酸エステル
類;スチレン類;ビニルエーテル類;ビニルエステル類
;N−ビニル複素環類;アリールエーテル類;アリルエ
ステル類等のモノマーを挙げる事ができる。The photocurable composition of the negative recording material used in the present invention includes a polymerizable and decolorizable compound having at least one vinyl group in the molecule and an electron-donating colorless dye. Refers to a compound that decolorizes a colored complex between a compound and an electron-accepting compound. Typical examples of these compounds include acrylic acid and its salts, acrylic esters, acrylamides; methacrylic acid and its salts, methacrylic esters, methacrylamides; maleic anhydride, maleic esters; itaconic acid, Monomers such as itaconic acid esters; styrenes; vinyl ethers; vinyl esters; N-vinyl heterocycles; aryl ethers; allyl esters can be mentioned.
【0016】これらの中で特に分子内に複数のビニル基
を有するモノマーが好ましく、例えば、トリメチロール
プロパンやペンタエリスリトール等のような多価アルコ
ールのアクリル酸エステルやメタクリル酸エステル;お
よびアクリレートまたはメタクリレート末端エポキシ樹
脂、アクリレートまたはメタクリレート末端ポリエステ
ル等がある。特に好ましい化合物の具体例としては、例
えばエチレングリコールジアクリレート、エチレングリ
コールジメタクリレート、トリメチロールプロパントリ
アクリレート、ペンタエリスリトールテトラアクリレー
ト、ジペンタエリスリトールヒドロキシペンタアクリレ
ート、ヘキサンジオール−1,6−ジメタクリレートお
よびジエチレングリコールジメタクリレート等である。
多官能モノマーの分子量については、約100〜約50
00が好ましく、より好ましくは、約300〜約200
0である。Among these, monomers having a plurality of vinyl groups in the molecule are particularly preferred, such as acrylic esters and methacrylic esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol; and acrylate or methacrylate terminals. These include epoxy resins, acrylate- or methacrylate-terminated polyesters, and the like. Specific examples of particularly preferred compounds include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hydroxypentaacrylate, hexanediol-1,6-dimethacrylate, and diethylene glycol dimethacrylate. methacrylate, etc. The molecular weight of the polyfunctional monomer is about 100 to about 50
00 is preferred, more preferably about 300 to about 200
It is 0.
【0017】これらの化合物の他に、光架橋性組成物と
して例えばポリケイ皮酸ビニル、ポリシンナミリデン酢
酸ビニル、α−フェニルマレイミド基をもつ光硬化性組
成物等を添加することができる。また、これらの光架橋
性組成物を光硬化性成分として用いてもよい。In addition to these compounds, photocurable compositions such as polyvinyl cinnamate, polycinnamylidene vinyl acetate, and α-phenylmaleimide group-containing photocurable compositions can be added as photocrosslinkable compositions. Moreover, you may use these photocrosslinkable compositions as a photocurable component.
【0018】更に、これらの化合物の他に、光硬化性組
成物の中には熱重合禁止剤を必要に応じて添加する事が
できる。熱重合禁止剤は、光硬化性組成物の熱的な重合
や経時的な重合を防止するために添加するもので、これ
により光硬化性組成物の調製時や保存時の化学的な安定
性を高めることができる。熱重合禁止剤の例として、p
−メトキシフェノール、ハイドロキノン、t−ブチルカ
テコール、ピロガロール、2−ヒドロキシベンゾフェノ
ン、4−メトキシ−2−ヒドロキシベンゾフェノン、塩
化第一銅、フェノチアジン、クロラニル、ナフチルアミ
ン、β−ナフトール、2,6−ジ−t−ブチル−p−ク
レゾール、ニトロベンゼン、ジニトロベンゼン、ピクリ
ン酸、p−トルイジン等が挙げられる。熱重合禁止剤の
好ましい添加量は、光硬化性組成物の全重量基準で0.
001〜5重量%であり、より好ましくは、0.01〜
1重量%である。0.001重量%未満では熱安定性が
劣り、5重量%を越えると感度が低下する。Furthermore, in addition to these compounds, a thermal polymerization inhibitor can be added to the photocurable composition as required. Thermal polymerization inhibitors are added to prevent thermal polymerization of photocurable compositions and polymerization over time, and this improves the chemical stability of photocurable compositions during preparation and storage. can be increased. As an example of a thermal polymerization inhibitor, p
-Methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t- Examples include butyl-p-cresol, nitrobenzene, dinitrobenzene, picric acid, p-toluidine, and the like. The preferable amount of the thermal polymerization inhibitor added is 0.00000000000000000000000000000000000000000000000,0000,0000,000,000,000,000,000 which is based on the total weight of the photocurable composition.
001 to 5% by weight, more preferably 0.01 to 5% by weight
It is 1% by weight. If it is less than 0.001% by weight, thermal stability will be poor, and if it exceeds 5% by weight, sensitivity will be reduced.
【0019】本発明の記録材料の光硬化性組成物は必要
に応じてマイクロカプセルに内包して使用してもよい。
例えばヨーロッパ特許第0223587号や上記特許を
参考にマイクロカプセルに内包させることができる。The photocurable composition of the recording material of the present invention may be used by being encapsulated in microcapsules, if necessary. For example, it can be encapsulated in microcapsules with reference to European Patent No. 0223587 and the above patents.
【0020】本発明の記録材料に係わる電子供与性無色
染料は従来より公知のトリフエニルメタンフタリド系化
合物、フルオラン系化合物、フエノチアジン系化合物、
インドリルフタリド系化合物、ロイコオ−ラミン系化合
物、ロ−ダミンラクタム系化合物、トリフエニルメタン
系化合物、トリアゼン系化合物、スピロピラン系化合物
、フルオレン系化合物など各種の化合物を使用できる.
フタリド類の具体例は米国再発行特許明細書第23,0
24号、米国特許明細書第3,491,111号、同第
3,491,112号、同第3,491,116号およ
び同第3,509,174号、フルオラン類の具体例は
米国特許明細書第3,624,107号、同第3,62
7,787号、同第3,641,011号、同第3,4
62,828号、同第3,681,390号、同第3,
920,510号、同第3,959,571号、スピロ
ジピラン類の具体例は米国特許明細書第3,971,8
08号、ピリジン系およびピラジン系化合物類は米国特
許明細書第3,775,424号、同第3,853,8
69号、同第4,246,318号、フルオレン系化合
物の具体例は特願昭61−240989号等に記載され
ている.The electron-donating colorless dyes used in the recording material of the present invention include conventionally known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds,
Various compounds can be used, such as indolylphthalide compounds, leukoolamine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds.
Specific examples of phthalides are given in U.S. Reissue Patent Specification No. 23,0.
No. 24, U.S. Pat. Specification No. 3,624,107, Specification No. 3,62
No. 7,787, No. 3,641,011, No. 3, 4
No. 62,828, No. 3,681,390, No. 3,
No. 920,510, No. 3,959,571, and specific examples of spirodipyrans are given in U.S. Patent Specification No. 3,971,8.
No. 08, pyridine-based and pyrazine-based compounds are disclosed in U.S. Patent No. 3,775,424 and U.S. Pat.
Specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989, etc.
【0021】これらの一部を開示すれば、トリアリール
メタン系化合物としては、3,3−ビス(p− ジメチ
ルアミノフェニル)−6−ジメチルアミノフタリド、3
,3−ビス(p− ジメチルアミノフェニル) フタリ
ド、3−(p− ジメチルアミノフェニル)−3−(1
,3ジメチルインドール−3− イル) フタリド、3
−(p− ジメチルアミノフェニル)−3−(2− メ
チルインドール−3− イル) フタリド、等があり、
ジフェニルメタン系化合物としては、4,4’− ビス
− ジメチルアミノベンズヒドリンベンジルエーテル、
N−ハロフェニル− ロイコオーラミン、N−2,4,
5−トリクロロフェニルロイコオーラミン等があり、キ
サンテン系化合物としては、ローダミン−B− アニリ
ノラクタム、ローダミン−(p−ニトリノ) ラクタム
、2−( ジベンジルアミノ) フルオラン、2−アニ
リノ−3−メチル−6− ジエチルアミノフルオラン、
2−アニリノ−3− メチル−6− ジブチルアミノフ
ルオラン、2−アニリノ−3− メチル−6−N− エ
チル−N− イソアミルアミノフルオラン、2−アニリ
ノ−3− メチル−6−N− メチル−N− シクロヘ
キシルアミノフルオラン、2−アニリノ−3− クロル
−6− ジエチルアミノフルオラン、2−アニリノ−3
− メチル−6−N− エチル−N− イソブチルアミ
ノフルオラン、2−アニリノ−6− ジブチルアミノフ
ルオラン、2−アニリノ−3− メチル−6−N− メ
チル−N− テトラヒドロフルフリルアミノフルオラン
、2−アニリノ−3− メチル−6− ピペリジノアミ
ノフルオラン、2−(o− クロロアニリノ)−6−ジ
エチルアミノフルオラン、2−(3,4− ジクロルア
ニリノ)−6−ジエチルアミノフルオラン、等があり、
チアジン系化合物としては、ベンゾイルロイコンメチレ
ンブルー、p−ニトロベンジルロイコメチレンブルー等
があり、スピロ系化合物としては3−メチル− スピロ
− ジナフトピラン、3−エチル− スピロ− ジナフ
トピラン3,3’− ジクロロ− スピロ− ジナフト
ピラン、3−ベンジルスピロ−ジナフトピラン、3−メ
チル− ナフト−(3−メトキシ− ベンゾ)−スピロ
ピラン、3−プロピル− スピロ− ジベンゾピラン等
があり、これらの電子供与性無色染料を必要に応じて1
種もしくは2種以上を混合して用いる事ができる。特に
、シアン、マゼンタ、イエロー用の電子供与性無色染料
しては米国特許第4,800,149号等を、イエロー
発色タイプとしては米国特許第4,800,148号等
を、シアン発色タイプとしては特開昭63−53542
号等を参考にできる。To disclose some of these, triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3
, 3-bis(p-dimethylaminophenyl) phthalide, 3-(p-dimethylaminophenyl)-3-(1
,3dimethylindol-3-yl) phthalide,3
-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl) phthalide, etc.
Examples of diphenylmethane compounds include 4,4'-bis-dimethylaminobenzhydrin benzyl ether,
N-halophenyl-leucoauramine, N-2,4,
5-trichlorophenylleucoolamine, etc., and xanthene compounds include rhodamine-B-anilinolactam, rhodamine-(p-nitrino)lactam, 2-(dibenzylamino)fluoran, and 2-anilino-3-methyl. -6- diethylaminofluorane,
2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-methyl- N-cyclohexylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-anilino-3
- Methyl-6-N-ethyl-N-isobutylaminofluorane, 2-anilino-6-dibutylaminofluorane, 2-anilino-3-methyl-6-N-methyl-N-tetrahydrofurfurylaminofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 2-(o-chloroanilino)-6-diethylaminofluorane, 2-(3,4-dichloroanilino)-6-diethylaminofluorane, etc. ,
Thiazine compounds include benzoyl leucomethylene blue and p-nitrobenzyl leucomethylene blue, and spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3,3'-dichloro-spiro- Dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)-spiropyran, 3-propyl-spiro-dibenzopyran, etc.
A species or a mixture of two or more species can be used. In particular, U.S. Patent No. 4,800,149 is used as an electron-donating colorless dye for cyan, magenta, and yellow, U.S. Pat. is Japanese Patent Publication No. 63-53542
You can refer to the number etc.
【0022】本発明の記録材料の電子供与性無色染料を
マイクロカプセル化する方法としては当業界公知の方法
を用いることができる。例えば米国特許第280045
7号、同28000458号に見られるような親水性壁
形成材料のコアセルベーシヨンを利用した方法、米国特
許第3287154号、英国特許第990443号、特
公昭38−19574号、同42−446号、同42−
771号に見られるような界面重合法、米国特許第34
18250号、同3660304号に見られるポリマー
の析出による方法、米国特許第3796669号に見ら
れるイソシアネートポリオール壁材料を用いる方法、米
国特許第3914511号に見られるイソシアネート壁
材料を用いる方法、米国特許第4001140号、同4
087376号、同4089802号に見られる尿素−
ホルムアルデヒド系、尿素ホルムアルデヒド−レゾルシ
ノール系壁形成材料を用いる方法、米国特許第4025
455号に見られるメラミン−ホルムアルデヒド樹脂、
ヒドロキシプロピルセルロース等の壁形成材料を用いる
方法、特公昭36−9168号、特開昭51−9079
号に見られるモノマーの重合によるイン シツ (i
n situ)法、英国特許第952807号、同9
65074号に見られる電解分散冷却法、米国特許第3
111407号、英国特許第930422号に見られる
スプレードライング法等がある。これらに限定されるも
のではないが、芯物質を乳化した後マイクロカプセル壁
として高分子膜を形成することが好ましい。本発明の記
録材料のマイクロカプセル壁の作り方としては特に油滴
内部からのリアクタントの重合によるマイクロカプセル
化法を使用する事が好ましい。即ち、短時間内に、均一
な粒径を持ち、生保存性にすぐれた記録材料として好ま
しいカプセルを得ることができる。[0022] As a method for microencapsulating the electron-donating colorless dye of the recording material of the present invention, methods known in the art can be used. For example, US Patent No. 280045
No. 7, a method using coacervation of a hydrophilic wall-forming material as seen in No. 28000458, US Pat. , 42-
Interfacial polymerization methods such as those found in U.S. Pat. No. 771, U.S. Pat.
18250, 3660304, isocyanate polyol wall materials as seen in U.S. Pat. No. 3,796,669, isocyanate wall materials as in U.S. Pat. No. 3,914,511, U.S. Pat. No. 4,001,140. No. 4
Urea found in No. 087376 and No. 4089802
Method using formaldehyde-based, urea-formaldehyde-resorcinol-based wall forming material, US Pat. No. 4025
Melamine-formaldehyde resin found in No. 455,
Method using wall-forming materials such as hydroxypropylcellulose, Japanese Patent Publication No. 36-9168, Japanese Patent Application Laid-Open No. 51-9079
In situ (i
n situ) method, UK Patent No. 952807, UK Patent No. 9
65074, the electrolytic dispersion cooling method, U.S. Pat.
111407, and the spray drying method as seen in British Patent No. 930422. Although not limited thereto, it is preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall. In order to form the microcapsule walls of the recording material of the present invention, it is particularly preferable to use a microencapsulation method by polymerizing a reactant from inside an oil droplet. That is, it is possible to obtain capsules, which are desirable as a recording material and have a uniform particle size and excellent storage stability, within a short time.
【0023】例えばポリウレタンをカプセル壁材として
用いる場合には多価イソシアネート及び必要に応じてそ
れと反応しカプセル壁を形成する第2の物質 (例えば
ポリオール、ポリアミン)をカプセル化すべき油性液体
中に混合し水中に乳化分散し次に温度を上昇することに
より、油滴界面で高分子形成反応を起こして、マイクロ
カプセル壁を形成する。このとき油性液体中に低沸点の
溶解力の強い補助溶剤を用いることができる。この場合
に、用いる多価イソシアネート及びそれと反応する相手
のポリオール、ポリアミンについては米国特許第328
1383号、同3773695号、同3793268号
、特公昭48−40347号、同49−24159号、
特開昭48−80191号、同48−84086号に開
示されており、それらを使用することもできる。本発明
の記録材料に用いるカプセルの平均粒子径は2μm以下
であり、特に解像度の点から0.5μm以下が好ましい
。またカプセルが小さすぎる場合には一定固形分に対す
る表面積が大きくなり多量の壁剤が必要となる。このた
め0.1μm以上が好ましい。For example, when polyurethane is used as the capsule wall material, a polyvalent isocyanate and, if necessary, a second substance that reacts with it to form the capsule wall (eg, polyol, polyamine) are mixed into the oily liquid to be encapsulated. By emulsifying and dispersing it in water and then increasing the temperature, a polymer formation reaction occurs at the oil droplet interface, forming a microcapsule wall. At this time, a co-solvent with a low boiling point and strong dissolving power can be used in the oily liquid. In this case, the polyvalent isocyanate used and the polyol and polyamine to be reacted with it are described in US Pat. No. 328
No. 1383, No. 3773695, No. 3793268, Special Publication No. 48-40347, No. 49-24159,
It is disclosed in JP-A-48-80191 and JP-A-48-84086, and these can also be used. The average particle diameter of the capsules used in the recording material of the present invention is 2 μm or less, and preferably 0.5 μm or less from the viewpoint of resolution. Also, if the capsule is too small, the surface area for a given solids content will be large and a large amount of wall material will be required. For this reason, the thickness is preferably 0.1 μm or more.
【0024】本発明の記録材料に係る、電子供与性無色
染料はマイクロカプセル中に溶液状態で存在してもよく
、また、固体の状態で存在してもよい。溶液状態で電子
供与性無色染料を存在させる場合は電子供与性無色染料
を溶媒に溶解した状態でカプセル化すればよい。この時
の溶媒の量は電子供与性無色染料100重量部に対して
1〜500重量部の割合が好ましい。The electron-donating colorless dye according to the recording material of the present invention may be present in the microcapsules in a solution state or in a solid state. When the electron-donating colorless dye is present in a solution state, the electron-donating colorless dye may be encapsulated in a state dissolved in a solvent. The amount of the solvent at this time is preferably 1 to 500 parts by weight per 100 parts by weight of the electron-donating colorless dye.
【0025】本発明の記録材料では保護層中にマット剤
を添加する事が好ましい。マット剤としては例えばシリ
カ、酸化マグネシウム、硫酸バリウム、硫酸ストロンチ
ウム、ハロゲン化銀などの無機化合物及びポリメチルメ
タクリレート、ポリアクリロニトリル、ポリスチレンの
ごときポリマー粒子や、カルボキシ澱粉、コーン澱粉、
カルボキシニトロフェニル澱粉などの澱粉粒子などがあ
り、粒子径が1ー20μmのものが好ましい。これらの
マット剤のなかではポリメチルメタクリレート粒子とシ
リカ粒子が特に好ましい。シリカ粒子としては例えばF
UJI−DEVISON CHEMICHAL L
TD.製のサイロイドAL−1、65、72、79、7
4、404、620、308、978、161、162
、244、255、266、150等が好ましい。マッ
ト剤の添加量としては2ー500mg/m2が好ましく
、特に好ましくは5ー100mg/m2である。In the recording material of the present invention, it is preferable to add a matting agent to the protective layer. Examples of matting agents include inorganic compounds such as silica, magnesium oxide, barium sulfate, strontium sulfate, and silver halide, polymer particles such as polymethyl methacrylate, polyacrylonitrile, and polystyrene, carboxy starch, corn starch,
Examples include starch particles such as carboxynitrophenyl starch, preferably those having a particle size of 1 to 20 μm. Among these matting agents, polymethyl methacrylate particles and silica particles are particularly preferred. Examples of silica particles include F
UJI-DEVISON CHEMICHAL L
TD. Thyroid AL-1, 65, 72, 79, 7
4, 404, 620, 308, 978, 161, 162
, 244, 255, 266, 150, etc. are preferred. The amount of the matting agent added is preferably 2-500 mg/m2, particularly preferably 5-100 mg/m2.
【0026】本発明の記録材料では感光・感熱層、保護
層等本発明の記録材料の各層に硬化剤を併用することが
好ましい。特に保護層中に硬化剤を併用し、保護層の粘
着性を低減する事が好ましい。硬化剤としては例えば、
写真感光材料の製造に用いられる「ゼラチン硬化剤」が
有用であり、例えばホルムアルデヒド、グルタルアルデ
ヒドのごときアルデヒド系の化合物、米国特許第363
5718号その他に記載されている反応性のハロゲンを
有する化合物、米国特許第3635718号その他に記
載されている反応性のエチレン性不飽和結合をもつ化合
物、米国特許第3017280号その他に記載されてい
るアジリジン系化合物、米国特許第3091537号そ
の他に記載されているエポキシ系化合物、ムコクロル酸
のようなハロゲノカルボキシアルデヒド類、ジヒドロキ
シジオキサン、ジクロロジオキサン等ジオキサン類ある
いは米国特許第3642486号や米国特許第3687
707号に記載されているビニルスルホン類、米国特許
第3841872号に記載されているビニルスルホンプ
レカーサー類、米国特許第3640720号に記載され
ているケトビニル類、あるいは又、無機硬化剤としてク
ロム明ばん、硫酸ジルコニウム、硼酸等を用いることが
できる。添加量としてはバインダーに対して0.5ー5
重量%が好ましい。このほか、保護層にはその粘着性を
低下させるためにコロイダルシリカを添加してもよい。
コロイダルシリカとしては例えば、日産化学製のスノー
テックス20、スノーテックス30、スノーテックスC
、スノーテックスO、スノーテックスN等が好ましい。
添加量としてはバインダーに対して5ー80重量%が好
ましい。また保護層には本発明に用いる記録材料の記録
材料の白色度をあげるための蛍光増白剤やブルーイング
剤としての青色染料を添加してもよい。In the recording material of the present invention, it is preferable to use a curing agent in each layer of the recording material of the present invention, such as the photosensitive/thermosensitive layer and the protective layer. In particular, it is preferable to use a curing agent in the protective layer in order to reduce the adhesiveness of the protective layer. Examples of hardening agents include:
"Gelatin hardening agents" used in the production of photographic light-sensitive materials are useful, such as aldehyde-based compounds such as formaldehyde and glutaraldehyde, and US Pat.
Compounds having a reactive halogen described in US Pat. No. 5718 and others, compounds having a reactive ethylenically unsaturated bond described in US Pat. No. 3,635,718 and others, compounds described in US Pat. No. 3,017,280 and others. Aziridine compounds, epoxy compounds described in U.S. Pat. No. 3,091,537 and others, halogenocarboxaldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, or U.S. Pat. No. 3,642,486 and U.S. Pat. No. 3,687.
707, vinyl sulfone precursors as described in U.S. Pat. No. 3,841,872, ketovinyls as described in U.S. Pat. No. 3,640,720, or alternatively chromium alum as an inorganic hardener. Zirconium sulfate, boric acid, etc. can be used. The amount added is 0.5-5 to the binder.
Weight percent is preferred. In addition, colloidal silica may be added to the protective layer to reduce its tackiness. Examples of colloidal silica include Snowtex 20, Snowtex 30, and Snowtex C manufactured by Nissan Chemical.
, Snowtex O, Snowtex N, etc. are preferred. The amount added is preferably 5 to 80% by weight based on the binder. Further, a fluorescent whitening agent or a blue dye as a bluing agent may be added to the protective layer to increase the whiteness of the recording material used in the present invention.
【0027】本発明の記録材料において、光硬化性組性
物の分散や電子供与性無色染料の分散およびカプセル化
は好ましくは水溶性ポリマー中で行われるが、本発明の
記録材料で好ましく用いることのできる水溶性ポリマー
としては、25℃の水に対して5重量%以上溶解する化
合物が好ましく、具体的には、ゼラチン、ゼラチン誘導
体、アルブミン、カゼイン等の蛋白質、メチルセルロー
ス、カルボキシメチルセルロース等のセルロース誘導体
、アルギン酸ソーダ、デンプン類(変性デンプンを含む
)等の糖誘導体、アラビアゴムやポリビニルアルコール
、スチレン−無水マレイン酸共重合体加水分解物、カル
ボキシ変性ポリビニルアルコール、ポリアクリルアミド
、酢酸ビニル−ポリアクリル酸共重合体の鹸化物、ポリ
スチレンスルホン酸塩等の合成高分子があげられる。
これらの中ではゼラチンおよびポリビニルアルコールが
好ましい。In the recording material of the present invention, the dispersion of the photocurable compound and the dispersion and encapsulation of the electron-donating colorless dye are preferably carried out in a water-soluble polymer. The water-soluble polymer that can be used is preferably a compound that dissolves 5% by weight or more in water at 25°C, and specifically includes proteins such as gelatin, gelatin derivatives, albumin, and casein, and cellulose derivatives such as methylcellulose and carboxymethylcellulose. , sodium alginate, sugar derivatives such as starches (including modified starches), gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, carboxy-modified polyvinyl alcohol, polyacrylamide, vinyl acetate-polyacrylic acid copolymer Synthetic polymers such as saponified polymers and polystyrene sulfonates can be mentioned. Among these, gelatin and polyvinyl alcohol are preferred.
【0028】本発明の記録材料において保護層、感光・
感熱層等本記録材料の各層のバインダーとしては上記水
溶性高分子およびポリスチレン、ポリビニルホルマール
、ポリビニルブチラール、アクリル樹脂:例えばポリメ
チルアクリレート、ポリブチルアクリレート、ポリメチ
ルメタクリレート、ポリブチルメタクリレートやそれら
の共重合体、フェノール樹脂、スチレン−ブタジエン樹
脂、エチルセルロース、エポキシ樹脂、ウレタン樹脂、
等の溶剤可溶性高分子あるいはこれらの高分子ラテック
スを用いることができる。これらの中ではゼラチンおよ
びポリビニルアルコールが好ましい。[0028] In the recording material of the present invention, a protective layer, a photosensitive
Binders for each layer of this recording material, such as the heat-sensitive layer, include the above-mentioned water-soluble polymers, polystyrene, polyvinyl formal, polyvinyl butyral, acrylic resins such as polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, and copolymers thereof. Coalescence, phenolic resin, styrene-butadiene resin, ethyl cellulose, epoxy resin, urethane resin,
Solvent-soluble polymers such as or latexes of these polymers can be used. Among these, gelatin and polyvinyl alcohol are preferred.
【0029】本発明の感光・感熱性記録材料の各層には
塗布助剤、帯電防止、スベリ性改良、乳化分散、接着防
止等種々の目的で、種々の界面活性剤を用いてもよい。
界面活性剤としては例えば非イオン性界面活性剤である
サポニン、ポリエチレンオキサイド、ポリエチレンオキ
サイドのアルキルエーテル等ポリエチレンオキサイド誘
導体やアルキルスルホン酸塩、アルキルベンゼンスルホ
ン酸塩、アルキルナフタレンスルホン酸塩、アルキル硫
酸エステル、N−アシル−N−アルキルタウリン類、ス
ルホコハク酸エステル類、スルホアルキルポリオキシエ
チレナルキルフェニルエーテル類等のアニオン性界面活
性剤、アルキルベタイン類、アルキルスルホベタイン類
等の両性界面活性剤、脂肪属あるいは芳香属第4級アン
モニウム塩類等のカチオン性界面活性剤を必要に応じ用
いる事ができる。Various surfactants may be used in each layer of the photosensitive/thermosensitive recording material of the present invention for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, and preventing adhesion. Examples of surfactants include nonionic surfactants such as saponin, polyethylene oxide, polyethylene oxide derivatives such as alkyl ethers of polyethylene oxide, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfate esters, N -Anionic surfactants such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylenyl phenyl ethers, amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines, fatty or A cationic surfactant such as aromatic quaternary ammonium salts can be used if necessary.
【0030】本発明の記録材料には、これまで述べた添
加剤をふくめ必要に応じて様々な添加剤を添加すること
ができる。例えば、イラジエーションやハレーションを
防止する染剤、紫外線吸収剤、可塑剤、蛍光増白剤、マ
ット剤、塗布助剤、硬化剤、帯電防止剤や滑り性改良剤
等の代表例はResearch Disclosur
e,Vol.176,1978年12月,Item
17643、および同 Vol.187,1979年
11月,Item 18716 に記載されている
。Various additives, including the additives mentioned above, can be added to the recording material of the present invention as required. For example, representative examples of dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, coating aids, curing agents, antistatic agents, and slipperiness improvers are listed in Research Disclosure.
e, Vol. 176, December 1978, Item
17643, and the same Vol. 187, November 1979, Item 18716.
【0031】本発明の記録材料の感光・感熱層用塗布液
や前述の各層用の塗布液は必要に応じて溶媒中に溶解せ
しめ、所望の支持体上に塗布し、乾燥することにより本
発明の記録材料が得られる。その場合に使用される溶媒
としては、水、アルコール:例えばメタノール、エタノ
ール,n−プロパノール、イソプロパノール、n−ブタ
ノール、sec−ブタノール、メチルセロソルブ、1−
メトキシ−2−プロパノール;ハロゲン系の溶剤:例え
ばメチレンクロライド、エチレンクロライド;ケトン:
例えばアセトン、シクロヘキサノン、メチルエチルケト
ン;エステル:例えば、酢酸メチルセロソルブ、酢酸エ
チル、酢酸メチル;トルエン、キシレン等の単独物及び
それらの2種以上の混合物が例として挙げられる。これ
らの中では水が特に好ましい。The coating liquid for the photosensitive/thermosensitive layer of the recording material of the present invention and the coating liquid for each layer described above are dissolved in a solvent as necessary, coated on a desired support, and dried. of recording material is obtained. Solvents used in this case include water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, methylcellosolve, 1-
Methoxy-2-propanol; halogenated solvents: e.g. methylene chloride, ethylene chloride; ketones:
Examples include acetone, cyclohexanone, methyl ethyl ketone; esters such as methyl cellosolve acetate, ethyl acetate, methyl acetate; toluene, xylene, and mixtures of two or more thereof. Among these, water is particularly preferred.
【0032】各層用の塗布液を支持体上に塗布するには
、ブレードコーター、ロッドコーター、ナイフコーター
、ロールドクターコーター、リバースロールコーター、
トランスファーロールコーター、グラビアコーター、キ
スロールコーター、カーテンコーター、エクストルージ
ョンコーター等を用いることができる。塗布方法として
はResearch Disclosure,Vol
.200,1980年12月,Item 20036
XV項を参考にできる。記録層の厚みとしては、0
.1μから50μが適当である。[0032] To apply the coating liquid for each layer onto the support, a blade coater, a rod coater, a knife coater, a roll doctor coater, a reverse roll coater,
A transfer roll coater, gravure coater, kiss roll coater, curtain coater, extrusion coater, etc. can be used. As a coating method, Research Disclosure, Vol.
.. 200, December 1980, Item 20036
You can refer to Section XV. The thickness of the recording layer is 0
.. A value of 1μ to 50μ is appropriate.
【0033】本発明の記録材料に適する支持体としては
ポリエチレンテレフタレートフィルム、三酢酸セルロー
ズフィルム、ポリエチレンフィルム、ポリスチレンフィ
ルム、ポリカーボネートフィルムなどの透明フィルムを
用いる事ができる。また、特に、重ね合わせて検版する
ときの最下層の感光・感熱性記録材料の支持体としては
紙、コーティッドペーパー、ラミネート紙、合成紙等の
支持体や、アルミニウム、亜鉛、銅などの金属の板等を
用いる事ができる。また、もちろん、上述の支持体の表
面に表面処理や下塗りや金属蒸着処理等の各種処理を施
したもの使用してもよい。支持体としてはResear
ch Disclosure,Vol.200,19
80年12月,Item 20036 XVII項
の支持体も参考にできる。また、これらの支持体は必要
に応じて表面にアンチハレーション層、裏面にスベリ層
、アンチスタッチク層、カール防止層、粘着剤層等目的
に応じた層を設けることができる。As a support suitable for the recording material of the present invention, transparent films such as polyethylene terephthalate film, cellulose triacetate film, polyethylene film, polystyrene film, and polycarbonate film can be used. In particular, as a support for the lowest layer photosensitive/thermosensitive recording material when inspecting the plates by overlapping them, supports such as paper, coated paper, laminated paper, synthetic paper, etc., and supports such as aluminum, zinc, copper, etc. A metal plate etc. can be used. Of course, the above-mentioned support may also be used after being subjected to various treatments such as surface treatment, undercoating, and metal vapor deposition. Resear as a support
ch Disclosure, Vol. 200,19
The support described in December 1980, Item 20036, Section XVII can also be referred to. Further, these supports can be provided with layers depending on the purpose, such as an antihalation layer on the surface and a slip layer, an anti-stack layer, an anti-curl layer, an adhesive layer, etc. on the back side, if necessary.
【0034】本発明の記録材料は、紫外光から可視光ま
での幅広い領域の光により高感度で記録できる。光源と
しては水銀灯、超高圧水銀灯、無電極放電型水銀灯、キ
セノンランプ、タングステンランプ、メタルハライドラ
ンプ、アルゴンレーザー、ヘリウムネオンレーザー、半
導体レーザー等の各種レーザー、LED、蛍光灯等幅広
い光源を使用できる。画像記録方法としては、リスフィ
ルムなどの通常使用されている印刷原稿の密着露光が望
ましいが、液晶画像や透明支持体上に形成した電子写真
画像等の原稿を用いた拡大露光、密着露光等の露光方法
も利用できる。The recording material of the present invention can record with high sensitivity using light in a wide range from ultraviolet light to visible light. As a light source, a wide range of light sources can be used, including mercury lamps, ultra-high pressure mercury lamps, electrodeless discharge mercury lamps, xenon lamps, tungsten lamps, metal halide lamps, various lasers such as argon lasers, helium neon lasers, and semiconductor lasers, LEDs, and fluorescent lamps. As an image recording method, contact exposure of commonly used printing originals such as lithographic film is desirable, but enlarged exposure, contact exposure, etc. using originals such as liquid crystal images or electrophotographic images formed on transparent supports are also preferable. Exposure methods can also be used.
【0035】本発明の記録材料は上記像様露光と同時ま
たは像様露光後に熱現像処理を行なう。この熱現像処理
における加熱方法としては従来公知の様々な方法を用い
ることができる。加熱温度は一般に80℃ないし200
℃、好ましくは100℃ないし160℃である。加熱時
間は1秒ないし5分、好ましくは3秒ないし1分である
。本発明の記録材料は熱現像処理後に全面露光を行ない
非硬化部分も光硬化させる事が好ましい。全面露光によ
り地肌部の発色反応と発色部の消色反応とが抑制される
ため画像の保存性が向上する。以下に本発明のカラー印
刷原稿の色校正方法について例示するが本発明はこれに
限定されるものではない。The recording material of the present invention is subjected to heat development treatment simultaneously with or after the imagewise exposure. As a heating method in this heat development treatment, various conventionally known methods can be used. Heating temperature is generally 80℃ to 200℃
℃, preferably 100℃ to 160℃. The heating time is 1 second to 5 minutes, preferably 3 seconds to 1 minute. The recording material of the present invention is preferably exposed to light over the entire surface after heat development treatment to photocure even the uncured portions. Full-surface exposure suppresses the color development reaction in the background area and the decolorization reaction in the color development area, thereby improving the storage stability of the image. The method for color proofing a color printed document according to the present invention will be exemplified below, but the present invention is not limited thereto.
【0036】[0036]
<塗布液の調製>
1.[電子供与性無色染料カプセルの調製]イエローカ
プセルの調製
1−a. 電子供与性無色染料(1)カプセルの調製
電子供与性無色染料(1)8.9gを酢酸エチル 1
6.9g に溶解し、タケネートD−110N(武田
薬品工業株式会社製) 20g とミリオネートM
R200 (日本ポリウレタン工業株式会社製)
2g を添加した。この溶液を、8%のフタル化ゼラ
チン42gと 10% のドデシルベンゼンスルホ
ン酸ナトリウム溶液 1.4g の混合液に添加し
、20℃で乳化分散し乳化液を得た。得られた乳化液に
水 14g と 2.9%のトリエチレンペンタ
ミン水溶液72g を加え、撹拌しながら60℃に加
温し、2時間後に電子供与性無色染料(1)を芯に含有
した、平均粒径 0.5 μmのカプセル液を得た
。
マゼンタカプセルの調製
1−b. 電子供与性無色染料(2)カプセルの調製
a.の電子供与性無色染料(1)を電子供与性無色染料
(2)に変更した以外はa.と同じ方法により平均粒径
0.5 μmの電子供与性無色染料(2)を内包
したカプセルを得た。
シアンカプセルの調製
1−c. 電子供与性無色染料(3)カプセルの調製
a.の電子供与性無色染料(1)を電子供与性無色染料
(3)に変更した以外はa.と同じ方法により平均粒径
0.5 μmの電子供与性無色染料(3)を内包
したカプセルを得た。
1−d. 電子供与性無色染料(4)カプセルの調製
a.の電子供与性無色染料(1)を電子供与性無色染料
(4)に変更した以外はa.と同じ方法により平均粒径
0.5 μmの電子供与性無色染料(4)を内包
したカプセルを得た。以下に、電子供与性染料(1)〜
(4)の構造式を示す。<Preparation of coating liquid> 1. [Preparation of electron-donating colorless dye capsule] Preparation of yellow capsule 1-a. Electron donating colorless dye (1) Preparation of capsules Electron donating colorless dye (1) 8.9g was mixed with ethyl acetate 1
Dissolved in 6.9 g of Takenate D-110N (manufactured by Takeda Pharmaceutical Co., Ltd.) and 20 g of Millionate M.
R200 (manufactured by Nippon Polyurethane Industries Co., Ltd.)
2g was added. This solution was added to a mixed solution of 42 g of 8% phthalated gelatin and 1.4 g of 10% sodium dodecylbenzenesulfonate solution, and emulsified and dispersed at 20° C. to obtain an emulsion. 14 g of water and 72 g of a 2.9% triethylenepentamine aqueous solution were added to the obtained emulsion, heated to 60° C. with stirring, and after 2 hours, the electron-donating colorless dye (1) was added to the core. A capsule liquid with an average particle size of 0.5 μm was obtained. Preparation of magenta capsules 1-b. Electron-donating colorless dye (2) Preparation of capsules a. except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (2). Capsules encapsulating the electron-donating colorless dye (2) with an average particle size of 0.5 μm were obtained by the same method as above. Preparation of cyan capsules 1-c. Electron-donating colorless dye (3) Preparation of capsules a. except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (3). Capsules encapsulating the electron-donating colorless dye (3) with an average particle size of 0.5 μm were obtained by the same method as above. 1-d. Electron-donating colorless dye (4) Preparation of capsules a. except that the electron-donating colorless dye (1) was changed to the electron-donating colorless dye (4). Capsules encapsulating the electron-donating colorless dye (4) with an average particle size of 0.5 μm were obtained by the same method as above. Below, electron donating dye (1) ~
The structural formula of (4) is shown.
【0037】[0037]
【化1】[Chemical formula 1]
【0038】2.[光硬化性組性物の乳化液の調製]2
−a. 光硬化性組性物(1)の乳化液の調製光重合
開始剤(1)0.2g と重合を促進するための助剤
2−メルカプトベンズイミダゾール 0.2g
の酢酸イソプロピル 3g の混合溶液に重合性
の電子受容性化合物(1) 5g を添加した。こ
の溶液を、13%ゼラチン水溶液 13g と
2%のドデシルベンゼンスルホン酸ナトリウム水溶液
2gとの混合溶液中に添加しホモジナイザー(日本精
機株式会社製)にて10000回転で5分間乳化し、光
硬化性組性物(1)の乳化液を得た。
2−b. 光硬化性組性物(2)の乳化液の調製光重
合開始剤(1) 0.2g と重合を促進するため
の助剤としてN−フェニルグリシンエチルエステル
0.2g の酢酸エチル 4g 溶液に電子受容
性化合物であるレゾルシン酸(1−メチル−2−フェノ
キシ)エチル 10gとトリメチロールプロパントリ
アクリレートモノマー 8g を添加した。この溶
液を、15%ゼラチン水溶液 19.2g と
水 4.8g と 2%ドデシルベンゼンスルホ
ン酸ナトリウム水溶液 2g との混合溶液中に添
加しホモジナイザー(日本精機株式会社製)にて100
00回転で5分間乳化し、光硬化性組性物(2)の乳化
液を得た。2. [Preparation of emulsion of photocurable composition] 2
-a. Preparation of emulsion of photocurable composition (1) 0.2 g of photopolymerization initiator (1) and 0.2 g of auxiliary agent for promoting polymerization 2-mercaptobenzimidazole
5 g of polymerizable electron-accepting compound (1) was added to a mixed solution of 3 g of isopropyl acetate. This solution was mixed with 13g of 13% gelatin aqueous solution.
2% sodium dodecylbenzenesulfonate aqueous solution
It was added to a mixed solution with 2g of the compound and emulsified for 5 minutes at 10,000 revolutions using a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to obtain an emulsion of photocurable assembled material (1). 2-b. Preparation of emulsion of photocurable composition (2) 0.2 g of photopolymerization initiator (1) and N-phenylglycine ethyl ester as an auxiliary agent to promote polymerization.
To a 0.2 g solution of 4 g of ethyl acetate were added 10 g of (1-methyl-2-phenoxy)ethyl resorcinate, which is an electron-accepting compound, and 8 g of trimethylolpropane triacrylate monomer. This solution was mixed with 19.2g of 15% gelatin aqueous solution.
It was added to a mixed solution of 4.8 g of water and 2 g of 2% sodium dodecylbenzenesulfonate aqueous solution and heated to 100 ml using a homogenizer (manufactured by Nippon Seiki Co., Ltd.).
Emulsification was carried out at 00 rpm for 5 minutes to obtain an emulsion of photocurable composition (2).
【0039】4.[感光・感熱層用塗布液の調製]シア
ン層
4−a. 感光・感熱層(1)用塗布液の調製電子供
与性無色染料(1)カプセル 4g と光硬化性組
性物(1)の乳化液12g と 15%ゼラチン水
溶液 12g とを混合し感光・感熱層(1)用塗
布液を調製した。
マゼンタ層
4−b. 感光・感熱層(2)用塗布液の調製電子供
与性無色染料(2)カプセル 4g と光硬化性組
性物(1)の乳化液12g と 15%ゼラチン水
溶液 12g とを混合し感光・感熱層(2)用塗
布液を調製した。
イエロー層
4−c. 感光・感熱層(3)用塗布液の調製電子供
与性無色染料(3)カプセル 4g と光硬化性組
性物(1)の乳化液12g と 15%ゼラチン水
溶液 12g とを混合し感光・感熱層(3)用塗
布液を調製した。
4−d. 感光・感熱層(4)用塗布液の調製電子供
与性無色染料(4)カプセル 4g と光硬化性組
性物(1)の乳化液12g と 15%ゼラチン水
溶液 12g とを混合し感光・感熱層(4)用塗
布液を調製した。
ネガ発色層
4−e. 感光・感熱層(5)用塗布液の調製電子供
与性無色染料(1)カプセル 1g と光硬化性組
性物(2)の乳化液10g とを混合し感光・感熱層
(5)用塗布液を調製した。4. [Preparation of coating solution for photosensitive/thermosensitive layer] Cyan layer 4-a. Preparation of coating solution for photosensitive/thermosensitive layer (1) 4g of electron-donating colorless dye (1) capsules, 12g of emulsion of photocurable compound (1), and 12g of 15% gelatin aqueous solution are mixed to form the photosensitive/thermosensitive layer. A coating solution for (1) was prepared. Magenta layer 4-b. Preparation of coating solution for photosensitive/thermosensitive layer (2) 4g of electron-donating colorless dye (2) capsules, 12g of emulsion of photocurable compound (1), and 12g of 15% gelatin aqueous solution are mixed to form the photosensitive/thermosensitive layer. A coating solution for (2) was prepared. Yellow layer 4-c. Preparation of coating solution for photosensitive/thermosensitive layer (3) 4g of electron-donating colorless dye (3) capsules, 12g of emulsion of photocurable compound (1), and 12g of 15% gelatin aqueous solution are mixed to form the photosensitive/thermosensitive layer. A coating solution for (3) was prepared. 4-d. Preparation of coating solution for photosensitive/thermosensitive layer (4) 4g of electron-donating colorless dye (4) capsules, 12g of emulsion of photocurable compound (1), and 12g of 15% gelatin aqueous solution are mixed to form the photosensitive/thermosensitive layer. A coating solution for (4) was prepared. Negative coloring layer 4-e. Preparation of Coating Solution for Photosensitive/Thermosensitive Layer (5) 1 g of electron-donating colorless dye (1) capsules and 10 g of emulsion of photocurable compound (2) are mixed to prepare a coating solution for photosensitive/thermosensitive layer (5). was prepared.
【0040】6.[ 保護層用塗布液の調製]6−a
. 保護層(1)用塗布液の調製10%ゼラチン水溶
液 4.5g と蒸留水 4.5g と 2
%ドデシルベンゼンスルホン酸ナトリウム水溶液 1
g と 2% 硬膜剤(1)水溶液 0.5g
とサイロイド 72(FUJI−DEVISON
CHEMICHALLTD.製)を塗布量が 5
0mg/m2となるだけの量とスノーテックスN1gと
を混合し保護層(1)用塗布液を調製した。以下に、重
合性の電子受容性化合物(1)、光重合開始剤(1)及
び硬膜剤(1)の構造式を示す。6. [Preparation of coating liquid for protective layer] 6-a
.. Preparation of coating solution for protective layer (1) 4.5 g of 10% gelatin aqueous solution, 4.5 g of distilled water, and 2
% sodium dodecylbenzenesulfonate aqueous solution 1
g and 2% hardener (1) aqueous solution 0.5g
and Thyroid 72 (FUJI-DEVISON
CHEMICHALLTD. Coating amount is 5
A coating solution for the protective layer (1) was prepared by mixing 1 g of Snowtex N in an amount sufficient to provide 0 mg/m2. The structural formulas of the polymerizable electron-accepting compound (1), the photopolymerization initiator (1), and the hardening agent (1) are shown below.
【0041】[0041]
【化2】[Chemical 2]
【0042】実施例1:ポジ型の感光・感熱性記録材料
感光・感熱層用塗布液(1)をコロナ処理を施した10
0μのポリエチレンテレフタレートフィルム上にコーテ
ィングバーを用いて塗布層の乾燥重量が 8g/m2
になるように塗布し、30℃で10分間乾燥した。その
上に保護層(1)用塗布液をコーティングバーを用いて
塗布層の乾燥重量が 2g/m2になるように塗布し
、30℃で10分間乾燥してシアン発色性のサンプルを
得た。得られた感光・感熱性記録材料にシアン用の画像
を現像したリスフィルムを通して2000W高周波点灯
型超高圧水銀灯(第日本スクリーン社製 プリンター
P627GA)からの紫外光で露光した。その後、12
0℃の熱板で5秒加熱したところ、鮮明なポジのシアン
画像が得られた。同様に感光・感熱層用塗布液(2)を
塗設した感光・感熱性記録材料を用い、更に、マゼンタ
用の画像を現像したリスフィルムを通して画像露光の後
現像して鮮明なポジのマゼンタ画像を得た。同様に感光
・感熱層用塗布液(3)を塗設した感光・感熱性記録材
料を用い、更に、イエロー用の画像を現像したリスフィ
ルムを通して画像露光の後現像して鮮明なポジのイエロ
ー画像を得た。同様に感光・感熱層用塗布液(4)を塗
設した感光・感熱性記録材料を用い、更に、黒用の画像
を現像したリスフィルムを通して画像露光の後現像して
鮮明なポジの黒画像を得た。得られた4枚のフィルムを
重ね合わせて鮮明なカラー画像を得た。Example 1: Coating liquid (1) for photosensitive/thermosensitive layer of positive type photosensitive/thermosensitive recording material was subjected to corona treatment.
The dry weight of the coating layer was 8g/m2 using a coating bar on a 0μ polyethylene terephthalate film.
It was applied and dried at 30°C for 10 minutes. A coating solution for the protective layer (1) was applied thereon using a coating bar so that the dry weight of the coating layer was 2 g/m 2 , and dried at 30° C. for 10 minutes to obtain a cyan coloring sample. The obtained photosensitive/thermosensitive recording material was exposed to ultraviolet light from a 2000 W high-frequency lighting ultra-high pressure mercury lamp (Printer P627GA manufactured by Dai-Nippon Screen Co., Ltd.) through a lithium film on which a cyan image had been developed. After that, 12
When heated for 5 seconds on a hot plate at 0° C., a clear positive cyan image was obtained. Using a photosensitive/heat-sensitive recording material coated with the photosensitive/heat-sensitive layer coating liquid (2) in the same manner, the image is exposed through a lith film on which a magenta image has been developed, and then developed to produce a clear positive magenta image. I got it. Similarly, using a photosensitive/heat-sensitive recording material coated with the photosensitive/heat-sensitive layer coating liquid (3), the image is exposed through a lith film on which a yellow image has been developed, and then developed to produce a clear positive yellow image. I got it. Similarly, using a photosensitive/heat-sensitive recording material coated with the photosensitive/heat-sensitive layer coating liquid (4), the image is exposed through a lith film on which a black image has been developed, and then developed to produce a clear positive black image. I got it. The resulting four films were superimposed to obtain a clear color image.
【0043】実施例2:ネガ型の感光・感熱性記録材料
実施例1と同様に感光・感熱層用塗布液(5)を塗設し
た感光・感熱性記録材料を用い、更に、シアン用の画像
を現像したリスフィルムを通して画像露光の後現像して
鮮明なネガのシアン画像を得た。Example 2: Negative type photosensitive/heat-sensitive recording material A photosensitive/heat-sensitive recording material coated with the coating liquid (5) for photosensitive/thermal layer in the same manner as in Example 1 was used, and a cyan layer coating liquid (5) was used. The image was exposed through developed lithographic film and then developed to obtain a clear negative cyan image.
【0044】[0044]
【発明の効果】本発明のカラー画像校正の方法を用いる
と、画像露光・熱現像という簡便な操作だけでカラー印
刷原稿を校正でき、この時、現像液やトナー等の現像剤
が不要で、作業環境を汚す心配の無い。また、本発明の
校正方法に用いる感光感熱性記録材料は高解像度・高画
質であるため高精度の校正を行う事ができる。[Effects of the Invention] By using the color image proofing method of the present invention, a color printed original can be proofread by simple operations such as image exposure and thermal development. There is no need to worry about polluting the work environment. Furthermore, since the photosensitive and heat-sensitive recording materials used in the calibration method of the present invention have high resolution and high image quality, highly accurate calibration can be performed.
Claims (3)
させた感光・感熱性記録材料を複数枚重ねてカラー印刷
原稿の色校正を行う方法に於いて、該感光・感熱性記録
材料が、露光により光硬化性組成物の露光部分が光硬化
した潜像が形成され、加熱により未硬化部分の重合性の
電子受容性化合物がその潜像に応じてマイクロカプセル
外からマイクロカプセル中に移動してマイクロカプセル
中の電子供与性無色染料を発色させて色画像を形成する
感光・感熱層を透明支持体上に設けた感光・感熱性記録
材料である事を特徴とするカラー印刷原稿の色校正方法
。Claim 1: A method for color proofing a color printed original by stacking a plurality of photosensitive/thermosensitive recording materials colored in colors corresponding to a positive color printed original, in which the photosensitive/thermal sensitive recording material is By exposure, a latent image is formed in which the exposed portion of the photocurable composition is photocured, and upon heating, the polymerizable electron-accepting compound in the uncured portion moves from outside the microcapsule into the microcapsule in accordance with the latent image. The color of a color printing original is characterized by being a photosensitive/thermosensitive recording material provided on a transparent support with a photosensitive/thermosensitive layer that forms a color image by coloring the electron-donating colorless dye in the microcapsules. Calibration method.
させた感光・感熱性記録材料を複数枚重ねてカラー印刷
原稿の色校正を行う方法に於いて、該感光・感熱性記録
材料が、露光により光硬化性組成物の露光部分が光硬化
した潜像が形成され、加熱により未硬化部分の重合性で
かつ消色性化合物がその潜像に応じてマイクロカプセル
外からマイクロカプセル中に移動してマイクロカプセル
中の電子供与性無色染料発色体を消色させて画像を形成
する感光・感熱層を透明支持体上に設けた感光・感熱性
記録材料である事を特徴とするカラー印刷原稿の色校正
方法。Claim 2: In a method for color proofing a color printing original by stacking a plurality of photosensitive/thermosensitive recording materials colored in colors corresponding to the negative color printing original, the photosensitive/thermosensitive recording material is By exposure, a latent image is formed by photocuring the exposed portion of the photocurable composition, and by heating, the polymerizable and color erasable compound in the uncured portion is transferred from outside the microcapsule into the microcapsule according to the latent image. Color printing characterized in that it is a photosensitive/thermosensitive recording material provided on a transparent support with a photosensitive/thermosensitive layer that moves and decolors the electron-donating colorless dye in the microcapsules to form an image. How to proofread the color of a manuscript.
記録材料がシアンもしくはマゼンタもしくはイエローも
しくは黒画像を形成する感光・感熱性記録材料である事
を特徴とするカラー印刷原稿の色校正方法。3. Color proofing of a color printing original, characterized in that the photosensitive/thermosensitive recording material according to claim 1 or 2 is a photosensitive/thermosensitive recording material that forms a cyan, magenta, yellow, or black image. Method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9208291A JPH04323657A (en) | 1991-04-23 | 1991-04-23 | Color proofing method for color printed original |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9208291A JPH04323657A (en) | 1991-04-23 | 1991-04-23 | Color proofing method for color printed original |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04323657A true JPH04323657A (en) | 1992-11-12 |
Family
ID=14044525
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9208291A Pending JPH04323657A (en) | 1991-04-23 | 1991-04-23 | Color proofing method for color printed original |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04323657A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5991438A (en) * | 1982-11-17 | 1984-05-26 | Fuji Photo Film Co Ltd | Photosensitive thermosensitive recording material |
JPS60119552A (en) * | 1983-12-01 | 1985-06-27 | Fuji Photo Film Co Ltd | Recording material |
JPH03119357A (en) * | 1989-10-02 | 1991-05-21 | Seiko Instr Inc | Photosensitive and heat-sensitive recording material |
JPH049947A (en) * | 1990-04-27 | 1992-01-14 | Seiko Instr Inc | Photosensitive and heat-sensitive transferring and recording device |
-
1991
- 1991-04-23 JP JP9208291A patent/JPH04323657A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5991438A (en) * | 1982-11-17 | 1984-05-26 | Fuji Photo Film Co Ltd | Photosensitive thermosensitive recording material |
JPS60119552A (en) * | 1983-12-01 | 1985-06-27 | Fuji Photo Film Co Ltd | Recording material |
JPH03119357A (en) * | 1989-10-02 | 1991-05-21 | Seiko Instr Inc | Photosensitive and heat-sensitive recording material |
JPH049947A (en) * | 1990-04-27 | 1992-01-14 | Seiko Instr Inc | Photosensitive and heat-sensitive transferring and recording device |
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