JPS6239423B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a cellular imaging material having a photosensitive layer on a planar support, containing a binder and a photosensitive diazonium salt, and without a coupler. Conventionally, the above-mentioned type of bubble image forming material is well known, and when the material is exposed to light by printing, nitrogen gas is generated in the photosensitive layer in the exposed area due to the photodecomposition of the photosensitive diazonium salt. When the material is heated, the gas thermally expands and forms small bubbles, which act to scatter light and form an image. On the other hand, as a method for producing the above-mentioned type of cellular image forming material, a polymer binder (for example, vinylidene chloride-acrylonitrile copolymer, methacrylonitrile-hydroxyethyl methacrylate copolymer, etc.) and a photosensitive diazonium salt with a low boiling point are combined. A solution prepared by dissolving in an organic solvent (e.g., methyl ethyl ketone, acetonitrile, etc.) is applied on a planar support in a layered manner (wet film thickness of about 50 to 100 microns),
A known method is to dry this for a long time under heat (usually at about 60 to 150°C) to form a thin dry film (film thickness of about 5 to 7 microns). Industrially, drying under heating for a long time is done by drying the support with the solution,
This is done by passing the material through a large dryer while conveying it using a large number of precisely controlled rolls. However, when forming a photosensitive layer by the above-mentioned conventional method, there are the following drawbacks. (a) Drying takes a long time and requires a large equipment space. (b) Organic solvent vapor is contained in a diluted state in a large amount of exhaust gas after drying, making it difficult to efficiently remove solvent from the exhaust gas. (c) Since drying takes a long time, precise operation control of each device including a large number of rolls for conveying the support with the solution is required. It is an object of the present invention to provide a method for producing cellular imaging materials that eliminates the drawbacks of these conventional methods. The present invention relates to a compound that exhibits cross-linking properties when irradiated with high-energy rays and a polymer compound that itself does not exhibit cross-linking properties when irradiated with high-energy rays and is suitable for impregnating a liquid containing a photosensitive diazonium salt that does not contain a coupler. (hereinafter referred to as an impregnating polymer compound) (hereinafter referred to as the liquid composition to be irradiated) is coated on the surface of the planar support in a layered manner, and then the liquid composition is coated with a high A method for producing a cellular image-forming material, which comprises forming an impregnated receptor layer by crosslinking and curing it by irradiating it with energy rays, impregnating it with the photosensitive diazonium salt-containing solution that does not contain a coupler, and drying it. It is. The planar support used in the present invention may be a support used in the production of conventionally known diazo image forming materials. For example, plastic film, synthetic paper, pulp paper, metal, glass, woven fabric,
Although nonwoven fabrics and the like may be used, plastic films excellent in physical strength, particularly dimensional stability, flatness, and transparency, such as biaxially oriented polyethylene terephthalate films, are particularly preferred. The photosensitive diazonium salt may be a photosensitive diazonium salt that has been used in the production of conventionally known diazo image forming materials, and examples of the photosensitive diazonium salt include 1-diazo-4-dimethylaminobenzene zinc chloride double salt. , or 1-diazo-4-morpholinobenzene tetrafluoroborate. In order to impregnate the impregnation-receiving layer with a photosensitive diazonium salt-containing liquid that does not contain a coupler (e.g., a phenolic compound, a compound having an active methylene group, etc.), a conventionally known impregnating device such as a liquid supply roll and a scraping member is used. An impregnating device consisting of the following can be used. The solvent in the photosensitive diazonium salt-containing liquid may be any solvent as long as it can dissolve the photosensitive diazonium salt and swell or somewhat dissolve the impregnated receiving layer. Examples of such a solvent include methyl ethyl ketone, Examples include acetonitrile, ethyl acetate, acetone, tetrahydrofuran, and dioxane. Drying after impregnating the impregnated receptor with the photosensitive diazonium salt-containing liquid is usually carried out at a temperature of 60 to 130°C. In the present invention, the impregnated receiving layer is formed by irradiating a liquid composition containing a compound exhibiting crosslinking properties and a polymer compound for imparting impregnating properties with high energy rays to crosslink and cure the composition. The high-energy rays referred to in the present invention are particularly preferably ultraviolet rays or electron beams. As a light source for ultraviolet irradiation equipment, 200nm ~
Metal halide-mercury lamps, low-pressure, high-pressure mercury lamps, etc. that emit ultraviolet light in the far-ultraviolet to near-ultraviolet ranges of 450 nm may be used. As an electron beam irradiation device, usually
Use one with a pressurizing voltage of 100 to 600 KeV and a current value of 10 to 100 mA. Compounds that exhibit crosslinking properties upon irradiation with high-energy rays have already been sufficiently disclosed in the literature. In the present invention, those known materials are used. Among these compounds, preferred are compounds that are liquid at room temperature and have 1 to 4 ethylenically unsaturated bonds but are not oligomers, or compounds that are liquid at room temperature and have 2 to 6 epoxy bonds. In particular, it is preferable to use compounds within the same type together. Furthermore, among these preferable compounds, those having a boiling point of 100°C or higher are particularly preferable. Among compounds that have 1 to 4 ethylenically unsaturated bonds but are not oligomers and are liquid at room temperature, examples of monomers having only one ethylenically unsaturated bond include methyl acrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl acrylate. Hydroxyethyl acrylate, tetrahydrofurfuryl acrylate,
Examples include phenoxyethyl acrylate or their methacrylates, as well as styrene, N-vinylpyrrolidone, and the like. Compounds that have 2 to 4 ethylenically unsaturated bonds but are not oligomers and are liquid at room temperature include, for example, ethylene glycol diacrylate, propylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol. Examples include pentaacrylate and their methacrylates. Examples of compounds that have 2 to 6 epoxy bonds and are liquid at room temperature include the following. Examples include 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, bisresorcinol tetraglycidyl ether, and epoxy novolak (epoxy equivalent: 172 to 181). As the polymer compound for imparting impregnating properties, vinyl copolymers containing vinylidene chloride as a main component and cellulose derivatives are particularly preferred, but other examples include homopolymers of vinyl monomers and formalin cocondensation resins. You can also do it. Among these, it is particularly preferable to select one of the above-mentioned vinyl copolymers or cellulose derivatives that also satisfies compatibility. Examples of the vinyl copolymer containing vinylidene chloride as a main component include copolymers of vinylidene chloride with acrylonitrile, vinyl chloride, alkyl acrylate, alkyl methacrylate, or vinyl acetate. The copolymerization rate of vinylidene chloride in these copolymers is preferably 80 to 95%. Examples of cellulose derivatives include the following. (a) Alkyl ester derivatives obtained by modifying cellulose with fatty acids, such as cellulose acetate, cellulose acetate butyrate, cellulose acetate isobutyrate, cellulose acetate propionate, (b) esters obtained by modifying cellulose with nitric acid. Derivatives such as cellulose nitrate, (c) ether derivatives obtained by modifying cellulose with dialkyl sulfate or alkyl halides, such as ethyl cellulose and propyl cellulose. Examples of formalin co-condensation resin include m-
There are xylene resins obtained by cocondensing xylene or mesitylene with formalin, and ketone resins obtained by cocondensing formalin with methyl ethyl ketone, cyclohexanone, methylcyclohexanone, acetophenol, etc. The impregnating polymer compound used in the present invention is essential for impregnating the impregnated receiving layer with the photosensitive diazonium salt-containing liquid. In carrying out the present invention, the amount of diazonium salt impregnated with respect to the weight of the impregnated receiving layer is usually 0.5 to 25
%, preferably 1% to 15%. When the liquid composition to be irradiated contains a liquid compound that has 1 to 4 ethylenically unsaturated bonds but is not an oligomer, the weight ratio of the polymer compound for imparting impregnating properties to the compound that exhibits crosslinking properties by high-energy rays. is preferably 20 to 80%, particularly preferably 25 to 68%. When containing a liquid compound having 2 to 6 epoxy bonds, the weight ratio is preferably 10 to 90%, particularly preferably 30 to 70%. When carrying out the present invention in an embodiment in which an irradiated liquid composition containing a liquid compound having 1 to 4 ethylenically unsaturated bonds but not an oligomer is irradiated with ultraviolet rays, photocrosslinking that generates radicals by ultraviolet irradiation is required. Preference is given to using activators. Examples of such photocrosslinking activators include benzoin, benzoin methyl ether, benzophenone, and benzyl. When carrying out the present invention in an embodiment in which a liquid composition to be irradiated containing a liquid compound having 2 to 6 epoxy bonds is irradiated with ultraviolet rays, Lewis
Using a photocrosslinking activator that generates an acid can
Practically advantageous. Suitable photocrosslinking activators that generate such Lewis acids are disclosed, for example, in U.S. Pat.
No. 3936557, Special Publication No. 14277, Special Publication No. 14277, Special Publication No. 52-
No. 14278, JP 52-14279, JP 52-30402
Disclosed in the No. For liquid compositions to be irradiated containing liquid compounds having 1 to 4 ethylenically unsaturated bonds but not oligomers, a small amount of a thermal polymerization inhibitor is added in order to prevent gelation during storage of the liquid composition to be irradiated. It is preferable to add. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether,
Examples include 2,6-di-tert-butyl-4-cresol and Kyuperon. However, copper salts, which are commonly used as thermal polymerization inhibitors, cannot be used because they accelerate the decomposition of diazonium salts. When using a liquid composition to be irradiated containing a liquid compound having 1 to 4 ethylenically unsaturated bonds but not an oligomer, the composition contains a crosslinked compound having 2 or more ethylenically unsaturated bonds. Preference is given to using oligomers. The crosslinkable oligomer is preferably one that has 1 to 4 ethylenically unsaturated bonds but is compatible with the liquid compound that is not an oligomer. Generally, those having a molecular weight of about 300 or more and 3000 or less are advantageously used. Examples of crosslinkable oligomers include polyester acrylates or polyester methacrylates obtained using low molecular weight polyesters, epoxy acrylates, epoxy methacrylates, urethane acrylates, urethane methacrylates, and the like. When using a liquid composition to be irradiated containing a liquid compound having 2 to 6 epoxy bonds, it is preferable to include a low molecular weight liquid compound having one epoxy bond as a diluent in the composition. Examples of the diluent include styrene oxide, which is known as a diluent for ordinary epoxy resins;
In addition to phenyl glycidyl ether, there are glycidyl methacrylate, allyl glycidyl ether, etc. each having one epoxy bond and one ethylenically unsaturated bond. According to the present invention described in detail above, unlike the conventional method, heat drying need only be performed to dry the photosensitive diazonium salt-containing liquid layer impregnated into the impregnated receiving layer. , has the following advantages. (a) Drying does not take a long time and does not require large equipment space. (b) The dryer can be small, the exhaust gas contains concentrated organic solvent vapor, and the solvent can be efficiently removed from the exhaust gas. (c) Since the transport and drying time is short, each device including the roller group for transporting the photosensitive diazonium salt-containing support can be made compact and its operation can be easily controlled. Therefore, according to the present invention, a cellular image forming material can be produced industrially advantageously. Examples are shown below. In the examples, "part" means part by weight (Kg), and "capacity" means volume (). The method for evaluating the characteristics of the developed and fixed material is as follows. The concentration was measured using a densitometer model TD-102 (F4.5) manufactured by Mac Beth, USA. The surface hardness of the developed and fixed material was expressed by pencil hardness. Adhesion was determined in accordance with JIS D-0202 using a so-called grid test. In other words, use a razor blade to make squares of 1 mm on each side on the surface of the developed and fixed material.
100 pieces (10 x 10) were made, cellophane tape was pressed onto the squares, rapidly peeled off, and the number of squares remaining on the surface was displayed. Therefore, 100/100 indicates that all 100 squares were not peeled off. Example 1 A liquid composition to be irradiated consisting of the following components was prepared. Tetrahydrofurfuryl acrylate (crosslinking agent) 46 parts diethylene glycol diacrylate (same as above)
17 parts poly(acrylonitrile-vinylidene chloride) (polymer compound for imparting impregnation properties) (Saran Viscosity 720cps (25℃)
A T-shirt with a mantle kept at 95℃ and kept at the same temperature.
Coated onto an untreated 75 micron biaxially stretched polyethylene terephthalate film using a die-type hopper, using a metal halide mercury lamp (80W/
The film thickness of the impregnated receptor layer cured using one cm) is
It was 12 microns. Next, 1-diazo-N,N-dimethylaminobenzene tetrafluoroborate (diazonium salt)
A diazonium salt solution consisting of 18 parts methyl ethyl ketone 295.7 volumes and acetonitrile 68.4 volumes was applied with a wire bar and dried at 80°C to 115°C to obtain a bubble image forming material. The above bubble image forming material was exposed to light and developed by heating at 100° C. for 20 seconds. Next, after exposing the entire surface to light, it was fixed by heating and stabilizing at 40°C. The evaluation results shown in Table 1 were obtained for the developed and fixed materials.

[Table] Example 2 Using a commercially available epoxy crosslinking agent composition and a photocrosslinking activator consisting of Lewis acid double salt of diazonium halide, the following crosslinking agent and polymeric compound for imparting impregnability were added and reconstituted. . Namely, Adeka Ultraset M-28-L1 (mixture of epoxy crosslinking agents having 6 or less epoxy bonds) (sold by Asahi Denka Co., Ltd.) 45 parts phenyl glycidyl ether (diluent) 30 parts 1,6-hexane Diol diglycidyl ether (crosslinking agent) 25 parts xylene resin (polymer compound for imparting impregnating properties)
(Nicanol H manufactured by Mitsubishi Gas Chemical Co., Ltd.) 21 parts Photocrosslinking activator PP for Adeka Ultraset
33 (sold by Asahi Denka Co., Ltd.) 4.3 parts The irradiated liquid composition [viscosity 98 cps (25° C.)] was subtracted. Coated in layers on a 75 micron thick biaxially oriented polyethylene terephthalate film.
A 3KW ultra-high pressure mercury lamp was irradiated for 45 seconds at a distance of 1m to create an impregnated receptor layer with a thickness of 6 microns. Next, a diazonium salt solution consisting of 31 parts of bis(1-diazo-N,N-dimethylaminobenzene)tetrachlorosincate, 372 parts of dioxane, and 129.5 volumes of acetonitrile was applied with a wire bar, and the foamed imaging material was dried at 80 to 110°C. Obtained. Expose the above bubble imaging material to light for 30-60 min at 100°C.
Developed by heating for seconds. Then, after full exposure, 400
It was fixed by heat stabilization at ℃. The evaluation results shown in Table 2 were obtained for the developed and fixed materials.

[Table] Example 3 A liquid composition to be irradiated consisting of the following components was prepared. Phenyl glycidyl ether (diluent) 19 parts glycidyl methacrylate ( ) 52 parts glycerin triglycidyl ether (crosslinking agent)
23 parts cellulose acetate butyrate (polymer compound for impregnation) (CAB551 manufactured by Kodak, USA)
0.01 30 parts ethylhydroxyethylcellulose (same as above)
(EHEC-Low manufactured by Hercules, USA) 13 parts The above composition [viscosity 860 cps (25°C)] was applied to a 75 micron biaxially stretched polyethylene terephthalate film that was subjected to subbing treatment, acceleration voltage 300 KeV,
It was cured by electron beam irradiation at a current value of 100 mA and a radiation absorption amount of about 1.5 Mrad to form an impregnated receptor layer with a film thickness of about 8 microns. The following diazonium salt solution was prepared, coated in layers with a wire bar coater, and dried at 80 to 110°C to obtain a cellular image-forming material. 1-Diazo-N-ethyl-N-benzylaminobenzene tetrafluoroporate 23 parts Dioxane 213 parts Acetonitrile 74 parts Toluene 18 parts The above bubble image forming material was exposed, developed and fixed in the same manner as in Example 2. The test results for the developed and fixed samples were as shown in Table 3.

【table】

Claims (1)

[Scope of Claims] 1. A compound that exhibits crosslinking properties when irradiated with high energy rays and which itself does not exhibit crosslinking properties when irradiated with high energy rays, and which is suitable for impregnating a liquid containing a photosensitive diazonium salt that does not contain a coupler. A liquid composition containing a polymer compound is applied onto the surface of a planar support, and then the liquid composition is cross-linked and cured by irradiation with high energy rays to form an impregnated receiving layer, which contains a coupler. A method for producing a cellular image-forming material, which comprises impregnating the material with the photosensitive diazonium salt-containing liquid and drying the material. 2. The method according to claim 1, wherein the compound exhibiting crosslinking properties upon irradiation with high-energy rays is a liquid compound having 1 to 4 ethylenically unsaturated bonds but not an oligomer. 3. The method according to claim 1, wherein the compound exhibiting crosslinkability upon high-energy ray irradiation is a liquid compound having 2 to 6 epoxy bonds. 4. A patent claim in which the polymer compound suitable for impregnation with a photosensitive diazonium salt-containing liquid that does not exhibit crosslinking properties upon irradiation with high-energy rays and does not contain couplers is a vinyl copolymer containing vinylidene chloride as a main component. The method described in item 1. 5. The method according to claim 1, wherein the polymer compound suitable for impregnation with a photosensitive diazonium salt-containing liquid that does not exhibit crosslinking properties and does not contain couplers when irradiated with high-energy rays is a cellulose derivative.