JPS58100127A - Negative type copying material and copying method - Google Patents

Abstract

PURPOSE:To form a visible image in a printing stage by using specified components which develop color under light and a negative type photopolymer. CONSTITUTION:An azide compound such as 4-diazo-N,N-dimethylaniline azide and a coupling component such as resorcin as components which develop color under light and a negative type photopolymer such as polyvinyl cinnamate as a photosetting component are dissolved in a solvent to prepare a photosensitive soln., and the soln. is applied to a support in 2-10mum thickness and dried. An undercoat layer of the components which develop color under light and a photopolymer layer may be formed on the support in order. A transparent or translucent negative original is brought into contact with the resulting copying material and irradiated with ultraviolet rays. The exposed part develops color and the photopolymer of the part is set. The unexposed part is then washed off with a developer to obtain a positive image.

Description

[Detailed description of the invention]

The present invention relates to a negative copying material useful for forming positive dye images of various tones simply by contact printing with ultraviolet irradiation, and a method for copying the same. Conventionally, a copying method has been known in which a positive image is formed from a negative original using a photochromic component that generates color by a coupling reaction caused by light and a photopolymer that becomes insoluble in a solvent after the photoreaction. There is. Various negative type copying materials have been put into practical use in this copying method. for example,
Copying material with 77+ tobolymer on a support and a photosensitive layer (1) for adding coloring agents such as dyes and pigments.The coloring agent is dispersed in a binder and undercoated on the support, and a layer of 70tobolymer is applied on the support. In order to form an image using this copying material, a negative original is brought into close contact with the copying material and the printing process is 8! By doing so, a cured part (cod light part) and an uncured part (unexposed part) of the 7 otobolimer are formed, and then the photopolymer and colorant in the unexposed part are removed with a solvent. Also known are copying materials in which colorless or almost colorless 7 otobolimers are provided on a support.
In the case of this copying material, after printing is carried out by closely contacting the original to the copying material, the sanded photopolymer in the non-exposed areas is removed with a solvent, and the exposed areas are colored with a dye solution. However, since all of these do not become visible images at the printing stage but become visible only at the developing stage, it cannot be determined whether the exposure amount at the time of printing 11 is appropriate until after the development. Therefore, it is impossible to adjust the "darkness" while looking at the 11 degrees of the image at the time of printing, and it is difficult to obtain a satisfactory image quality. In particular, in order to improve work efficiency, it is difficult to obtain a satisfactory image quality. This becomes a problem when developing the copy material.Furthermore, the capri generated during storage of the copying material cannot be known until after development, making it difficult to check during the process.Furthermore, the photosensitive layer contains 7 otobolimer. If colorants such as black, yellow, brown, etc. that absorb light in the range are included, the sensitivity will be impaired.As a copying material that compensates for the drawbacks of the above-mentioned copying materials, Japanese Patent Publication No. 51-4045
Publication No. 2 describes a copying material using an azide compound that can sometimes develop color and form a visible image during printing. Although Maro has made it possible, it is not satisfactory, and furthermore, the color tone of the resulting image is limited to brown. To adjust the image tone to the desired tone,
When dyes and pigments are used, sensitivity decreases as described above. Therefore, the present invention solves the following drawbacks of the conventional technology.More specifically, printing forms a visible image in stages, makes it possible to check the exposure amount each time, and prints in a wide range of tones. This paper describes the negative copying materials and copying methods that make it possible to produce images. Furthermore, it is an object of the present invention to provide a copying material in which fog generated during storage can be easily detected. That is, the present invention achieves the above-mentioned runner-up points at once by using a negative copying material characterized by containing an azide compound and a coupling component as a photochromic component and a negative photopolymer as a photocurable component. It is resolved. To form an image using the negative copying material of the present invention, a negative original is brought into close contact with the negative copying material and subjected to ultraviolet irradiation and contact printing to form an azo dye image;
Next, the coloring component and the negative photopolymer in the non-exposed area are removed by swelling or dissolving. The color-forming component and 7-tobolimer may coexist in one layer, or it may be a two-layer type in which a subbing layer is provided with the color-forming component and one layer of 74-tobolimer is provided thereon. The present invention will be described in detail below. □ As the support, any conventionally known support such as paper, plastic film, plastic plate, synthetic paper, cloth, metal, etc. can be used. As the azide compound, the following azides of diazo compounds commonly used in diazo type copying materials can be used. 4-Diazo-N, N-dimethylaniline, 4-
Diazo-N, N-diethylaniline, 4-diazo-
N-ethyl-N-β-hydroxyethylaniline,
4-Diazo-N, N-bis-β-hydroxyethylaniline, 4-diazo-N ~methyl-N-β
-Hydro 4゛sitepuraniline, 4-diazo-N-Jthyl-N-β-hydroxyethylaniline, 4-diazo-N, N-diethylaniline, 4-diazo-2-
Chloro-N, N-diethylaniline, 4-diazo-2-medyl-N, N-diethylaniline, 4-diazo-2-iodo-N, N-diethylaniline, 4-diazo-2-trifluoroDMebluN
, N-diethylaniline, 4-diazo-N-ethyl-N-benzylaniline, 4-diazo-N-methyl-N-benzylaniline, 4-diazo-2゜5-
Dib1~xy-N, N-diethylaniline, 4-diazo-2,5-jethoxy-N-benzoylaniline, 4-diazo-2,5-di1to4-cyN-TchiruN
-benzoylaniline, 4-diazo-2,5-shedoxy-N-benzoylmethyl7niline, J 4-diazo-2-chloro -5-methoxy-N-benzoylaniline, baradiazodiphenylamine, 4-diazo-2, 5,4°-trietho-1 sidiphenylamine, 4-diazo-2,5,4°-1-triethyl-[t-4]
Sidiphenyl, 4,4′-bisdiazo-2,2′
, 5,5'jt-lahydroxyschiff I nylmethine, bisthia/-3,3'-dichloro-5,5'-
Dimethoxybenbudine, 4-diazo-2,5-dimethoxyphenyl 1pur→Jrufu 1ide, 4-diazo-2
, 5-die 1 heoxy-4' ~ methylschiff I nyl sulfide, 4-diazo-2,5-dimethoxy-N'''
-phenylmorpholine, 4-diazo-2,5-shedoxy-N-phenylmorpholine, 4-diazo-2,
5-Jib

[~A1 Cc-phenylmorpholine, 4
-Diazo-2-j). °″7−N −7”=Rvf−i
f:,)Lyl” phosphorus, 4-diazo-N-phenylpiperidine, 4-diazo-N-phenylpyrrolidine, 4-diazo-2,5-n-buty-oxy, -N-phenylpiperidine, 4-diazo-2 -Azide compounds or diazide compounds such as -methyl-N-phenylpyrrolidine and 4-diazo-2-methoxy-N-phenylpyrrolidine.In addition, the coupling components used in combination with the azide compounds may also be the following conventional coupling components: Any of those used in diazo-type copying materials can be used: resorcin, phloroglucin, resorcin monohydroxyethyl ether, 2-hydroxydimethylphenol, β-(2-hydroxyphenyl)-propionic acid. , 2.5-Tumef-4-(N-dimethylamitumedel)-phenol, metahydroxy-acetanilide, 2゜5-dimethyl-4-mol 7-v linomethylphenol, 2-methyl-5-isopropyl -4
-morpholinomethylphenol, 3.3-. 5-trihydroxydiphenyl, 2.2-. 4.4′ −
Tetrahydroxydiphenyl, 2.2-. 4.4′
-Tetrahydrooxydiphenyl sulfide, -Hydroxyphenylurea, 2,3-dioxypphthalene, β-naphthol, α-nophthol, 1,6-cyoxynapht4talene, 2,7-diAxy Naphthalene, 2
．． 3-Dioxynaphthalene-6-sulfonic acid, 2-naphthol-3,6-disulfonic acid, 2.1-dihydro-quaternary sinaphthalene-3,6-disulfonic acid, 2.7-
Dihydroxynaphthalene-3-sulfonic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-3-
naphthoic acid -N-β-human 0oxy1 tyl ama,
ido, 2-human 0711cy 3-naphthoic acid-N,
N-bis-β-hydroxyethylamide, 2
- and droxy-3-naphthoic acid-N-n-pro and rumorpholinoamide, 2-hydroxy-3-naphtho]-acid anilide, 2-hydroxy-3-naph+, ■1
111-2'-Methylanilide, 8-hydroxy-12-hydroxy-acid-hydroxyethylamide, 1-naphthol-3-(N-β-hydroxyl,)-sulfonamide, 1-phenyl -3-methylpyrazolone, 1-phenyl-3-carboxybira,
Zo[l], cyanoacetanilide, cyanoacetyl, etc. Negative type as a photocurable component 4) - The polymer must be soluble in organic solvents and water before photoreaction, and become insolubilized after photoreaction. Many photosensitive polymers such as the compounds listed below are used. Examples of the diazonium salts include p-diazosifinylamine condensate with formaldehyde, p-quinonediazide, and p-quinonediazide.
-Imino: 1 nondiazide, etc. Further, as the azide compound, p-phenylenebisazide, p-azidobenzophenone, 4.4=-diazidebenzophenone, 4
．． 4'-diazidodiphenylmethane, 4.4'-diazidostilbene, 4.4'-diazidochalcone,
2.6-di(4'-azidobenzal)cyclohexanone, 2. Tri-(4'-azidobenzal)-
4-methylcyclohexanone, 1-azidopyrene, 4,
4'-Diazidostilbene-2,2=-sodium disulfonate, 1,5-di-1-sitonaphthalene-
- There are sodium 3,7-disulfonates, etc., and among these azide compounds, organic solvent soluble types are used by mixing with natural rubber, synthetic rubber, cyclized rubber, novolak resin, etc. In addition, water-soluble types are used by mixing with polyvinyl alcohol, polyvinylpyrrolidone, cyahidone acrylamide, methylcellulose, vinyl alcohol and maleic acid copolymer, vinylfluorol and acrylamide copolymer, and water-soluble polyvinyl butyral. It will be done. Further, examples of polymers having an azide group in the molecule include polyazidohinyl benzoate, polyazidophthal-plated vinyl, and polyvinylazidobenzal acetal. Examples of photopolymers with a simpmoyl group as a photosensitive group include polyvinyl cinnamate and polyvinyl alcohol cinnamylidene acetate nysdel g! There are conductors, and specific examples include polyvinyl cinnamylidene acetate, polyvinyl cinnamate cinnamylidene acetate, polyvinyl ethoxymethyl carbamate cinnamylidene acetate, polyvinyl acetate cinnamylidene acetate, and the like. Other examples include those having an acryloyl group, arcdylamides, acrylates, those having a styryl pyridinium group, and those having a styryl ketone group. In addition to the above-mentioned components, binders may also be used in the photosensitive material (1) of the present invention, such as polydonyl alcohol oxymethylcellulose, human [14-sib0-bilulose, methylcellulose, ethylcellulose, cellulose 7-cedate, Hill [1-sp[J Bi-A-based, cellulose butyrate, cellulose nitrate, polyvinyl acetate, polysprene, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylic acid-■al, bomethacrylic acid ester, W# Vinyl/vinyl chloride co-
compound, polyethylene, ethylene/vinyl acetate polymer,
Styrene/acrylic ester copolymer, vinyl acetate/
Any binder soluble in water, alkaline aqueous solution, or solvent can be used, such as crotonic acid copolymer, sulcine/maleic acid copolymer, etc. However, the binder must be selected depending on the photopolymer and developer used. For example, if water is used in the developer, a bamboo binder is used as the soil, and a water-insoluble binder or other water-resistant agent such as melamine, formalin, etc. is used as an auxiliary agent to impart appropriate water resistance. . As other additives, alkaline substances can also be used to promote color development. In the production of the negative copying material of the present invention, in the case of a one-piece type in which A topolyar, an azide compound, and a coupling component are contained in the same layer, W is used to dissolve these components.
A photosensitive solution is prepared by dissolving the photosensitive solution in a medium (using a mixed solvent if necessary), and the photosensitive solution is coated on a support and dried. The amount of coating is not particularly limited [but usually the thickness after drying is 2 to 10
μf? It is best to keep it at a certain level. In addition, in the case of the dual type, in which the photopolymer and the coloring component are contained in separate tubes, first make the liquid for the photochromic tube and apply it onto the support.
Dry 1. The coating method is not particularly limited, but the thickness after drying is preferably 1 to 5 g. Next, apply a negative type 7 otobolimer solution to the photochromic layer.
Apply and dry. In this case, in order to prevent the photocoloring layer from dissolving during application of the photopolymer solution, it is necessary to select a binder composition for the photocoloring layer that is difficult to dissolve in the solvent of the autopolymer solution. Although there is no particular limitation on the amount of photopolymer layer applied, it is preferable that the thickness after drying be 2 to 10 microns. To form an image using the negative copying material of the present invention thus prepared, a transparent or translucent negative Wt document is brought into close contact with the copying material and irradiated with ultraviolet rays. This baking is a process, and the non-exposed area of the polymer maintains a T9 quality that is UF8-recognized by solvents, and the photochromic component does not develop any color. On the other hand, the photopolymer in the exposed area hardens and becomes insoluble in the solvent, producing a photochromic component number. Next, the photopolymer in the unexposed area and the uncolored photochromic component are washed away with a developer (appropriate one of water, alkaline aqueous solution, or organic solvent type is selected and used depending on the type of photopolymer and photochromic component). Particularly)
[A clear positive image can be obtained. As in the iXt process, in the product of the present invention, color development 11i11 appears at about the printing number 2, and overexposure or underexposure can be determined at this point. Therefore, it is easy to work with and there are no failures due to poor exposure. The present invention will be explained below with reference to examples. Example 1 A photosensitive liquid having the following composition was applied to the matte surface of a 106 μm thick polyester film subjected to sand matte processing to obtain a negative copying material. The coating amount is 4 in terms of film thickness after drying.
It was μ. 1-? Cytopyrene 2 parts by weight Resorcinol 1 part by weight FJNol novolac resin 10 parts by weight Mebru ethyl ketone
When 50 parts by weight of transparent negative originals were placed on top of each other using a negative air printer (equipped with a chemical lamp) and irradiated with ultraviolet light for 1 minute, a brown positive image appeared. When this was then immersed in a vat containing a 1% aqueous solution of caustic soda for about 1 minute, the non-exposed areas were dissolved and a clearer brown positive image was obtained. Example 2 Thickness 10011 treated with 5% trichloroacetic acid aqueous solution
A photosensitive liquid having the following composition was applied to a polyester film to form a negative copying material of 19K. The coating thickness after drying was 5 μm. 4-azido-N,N-diethylaniline 1ψpart 2,3-dihydroshinaphthalene 11aH! 1 polyvinyl cinnamate 2 part cyclo ↑ Sanon 301 part methyl ebructone
When a 20-weight transparent negative original was placed in close contact with the original and irradiated with a pressure mercury lamp for 2 minutes, a bluish-purple positive image appeared. Next, when this was treated with trichlene, the non-exposed areas were dissolved and a clear blue-purple positive color was obtained! 1iIII was obtained. Example 3 A photochromic layer solution having the following composition was applied to a poly 1 sulfur film treated in the same manner as in Example 2, and the photochromic layer was first graded. The coating amount was 3 μm in thickness after drying. 4-Azide; 1 part by weight of N,N-diethylaniline 2.3-dihyde [koxyt-phthalene 1 part by weight Cellulose ahitate butyrate 5 parts by weight, 50 parts by weight of L-dihyrosolp Furthermore, the following composition was applied on the photochromic layer. A photo-curing layer is established by applying the photo-curing layer liquid. The coating amount was 5 μm in thickness after drying. Polyvinyl cinnamate 2ψms chloropene 15 parts 1 part toluene
35 parts by weight When a negative original was copied in the same manner as in Example 2 using the negative type copying material thus prepared, excellent binding similar to that in Example 2 was obtained. Example 4 Synthetic paper 1bo FP110 (manufactured by Tamago Yuka Synthetic Paper F Co., Ltd.) was coated with a liquid having the following composition to form a photochromic layer. Painted tI
j l was 2μ in thickness after drying. 4.4' ~Diazidospurpene-sodium 2,2-disulfonate 1 part by weight polyvinyl alcohol (
(degree of curing 99%, average polymerization 111,700) 3 Nakaibe polyvinyl acetate emulsion (solid content 50%) 2 parts by weight Noro-0 glucine 1 weight 1 part water
Further, a photocuring layer was provided on top of this photochromic layer by applying a liquid having the following composition. The coating amount was 4 μm in thickness after drying. Polyvinyl alcohol (degree of saponification 80.5%, degree of uniformity 500) 100 f[tβ-oxy 1 del methacrylate 1 part ethylene glycol methacrylate 5 fpHS part benzoin isopropyl ether 2.5 parts water 8
When the oφ Shimabe negative original was placed in close contact with the original and ultraviolet rays were irradiated (about 1 minute with a pressure mercury lamp), a dark brown positive image was obtained. Then, add tap water to the sponge and wipe the surface for 1 hour. The Jl exposed area swells and dissolves, revealing the white side of the synthetic paper.
A clearer positive image is created. Patent applicant Ricoh Co., Ltd. Agent Patent attorney Hideomi Komatsu

Claims (2)

[Claims] (1) A negative copying material characterized by containing an azide compound and a coupling component as a photochromic component, and a negative photopolymer as a photocurable component. (2) A negative original is closely attached to a negative copying material containing an azide compound and a coupling component as a photochromic component and a negative photopolymer as a photocurable component, and subjected to contact printing 4J treatment by ultraviolet irradiation to form an azo A copying method characterized in that a dye image is formed, and then the coloring component and the negative photopolymer in unexposed areas are removed by swelling or dissolving.