JPS5968298A - Photosensitive heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To enhance oil resistance, chemical resistance or the like, by adding a fluoro resin into a photosensitive layer, in a photosensitive heat-sensitive recording material provided with a heat-sensitive layer comprising an ammonium salt of a water-insoluble resin or the like and a photosensitive layer comprising a light-crosslinkable substance. CONSTITUTION:The heat-sensitive layer comprising at least one selected from the group consisting of particles of a thermoplastic resin such as polyvinyl acetate or polystyrene, a heat-solidifiable protein such as a protein single body (e.g., albumin) or a protein-containing substance and an ammonium salt or amine salt of a water-insoluble resin and a light-to-heat converting substance such as carbon black or iron powder in a ratio of 1:10-50 (by weight) is provided on a base. Then, the photosensitive layer comprising a light-crosslinkable photosensitive substance capable of undergoing a crosslinking reaction by absorbing light such as a diazonium salt or an azide compound and a fluoro resin such as polytetrafluoroethylene in a ratio of 1:0.2-1 (by weight) is provided on the heat- sensitive layer. Each of the heat-sensitive layer and the photosensitive layer may contain a binder in a quantity of up to 90wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a light and heat sensitive recording material in which a latent image is formed by light and heat.

Conventionally, ionomer tt1. and a photothermal converting material such as oil particles, water-soluble resin, car-in black, or iron powder that absorbs light and converts it into heat as an active ingredient (Japanese Unexamined Patent Application Publication No. 56-148590) ), in which phenolic resin particles were used instead of the ionomer resin in the recording paulownia wood (Japanese Unexamined Patent Publication No. 56-148+589), alcohol-soluble polyamide and a coloring agent were placed on the support to view it as a colored image. A colored layer whose main component is a colored layer and a photosensitive layer whose main component is an alcohol-soluble photocrosslinkable photosensitive substance (photoresist) is provided on top of the colored layer (Utility Model No. 55-16
4647) etc. are known. Among these, the heat-sensitive type melts or thermally crosslinks the ionomer resin or phenol resin in the exposed area by applying infrared rays as an image thermal light, making this area water-releasable or insolubilized, and then returning to the original water-soluble non-light-emitting area. When removed by dissolving VC in a developer (water), an image is formed from K, and the photosensitive type uses ultraviolet rays to form an image
When exposed to light, the photosensitive material in the exposed area is photo-crosslinked, creating a difference in solubility in the developer (alcohol in this case) between the source area and the non-exposed area, as in the case of heat-sensitive types. Thereafter, an image is formed by dissolving and removing the non-fogged areas in a developer. However, in the case of heat-sensitive type, when irradiated with infrared rays,
Due to the diffusion of heat caused by the photothermal converting substance, it has drawbacks such as the inability to obtain high-resolution images, the strength of the film, that is, the heat-sensitive layer, and the low oil resistance and chemical resistance of the film. In this case, the colored layer is also soluble in the developer, so the colored layer in one image area is side-etched during development; this has the disadvantage that the reproducibility of points and lines (hereinafter referred to as halftone dot reproducibility) is particularly poor. Ta.

Therefore, the present inventor first developed an ammonium salt or amine salt of a water-insoluble resin, a thermocoagulable protein, or a thermoplastic resin particle (vinyl resin, Nozelac fat, linear polyester, etc.) and a photothermal converting substance. A heat-sensitive layer mainly composed of
A light and heat sensitive recording material (Japanese Patent Application Nos. 157-43595, 57-43596, 57-153399, etc.) was proposed in which photosensitive layers containing photocrosslinkable photosensitive substances as the main component were sequentially provided, but they were not water resistant. The properties, oil resistance, and chemical resistance are still not fully satisfactory.

An object of the present invention is to form a high-resolution image.

It is an object of the present invention to provide a light and heat sensitive recording material which has excellent film strength, oil resistance and chemical resistance and is highly sensitive.

In other words, the photosensitive and heat sensitive R+2 recording material of the wood invention contains on a support Ka), plastic resin particles, thermocoagulable proteins, and ammonium salts of water-insoluble resins that can react with ammonia or amines to form water-soluble ammonium salts or amine salts. A heat-sensitive layer mainly composed of at least one selected from the group consisting of amine salts and h) a photothermal converting substance that absorbs light and converts it into heat, and a photo-crosslinkable photosensitive substance on the layer as a main component A light and heat sensitive recording material comprising sequentially provided photosensitive layers is characterized in that the photosensitive layer further contains a fluororesin.

The principle of forming an image (Cf1J image) using the recording material of Wood's invention is as follows. In other words, if the photothermal converting substance absorbs light in the wavelength range to which the photosensitive material is sensitive, by simply exposing the recording material to this light, the photothermal converting substance absorbs light in the wavelength range to which the photosensitive material is sensitive. The photosensitive material in the external light area of the photosensitive layer is cross-linked by sequentially exposing it to light that the photothermal converting material can absorb (usually heat rays such as infrared rays), provided that it does not absorb this light. At the same time as the reaction, the photothermal converting substance in the heat-sensitive layer below is heated to melt the coexisting thermoplastic resin particles, or the thermocoagulable protein is thermally coagulated, or the ammonium salt or amine salt resin is converted into ammonia. Alternatively, by liberating the amine, a developing solution (water, alkaline aqueous solution, etc.) is applied between the exposed area and the non-p' source area of the photosensitive layer and heat-sensitive layer.

This creates a difference in solubility in organic solvents, etc.).

The image area thus formed has excellent water repellency, oil repellency, and chemical resistance due to the excellent water repellency, oil repellency, and chemical resistance of the fluororesin contained in the photosensitive layer.

Next, the materials used in the wood invention will be explained. First, the photo-crosslinkable photosensitive material used in the photosensitive layer may be any material as long as it absorbs light and undergoes a cross-linking reaction. Polymers and polymers having cinnamoyl groups in their molecules are known. Diazonium salts include paraformaldehyde condensate of p-diazodiphenylamine and p-quinonediazide.

Examples include p-iminoginone diazide. Examples of the azide compounds include p-phenylene vinyl azide, p-azidobenzophenone, 4,4'-cytobenzophenone,
4,4'-Diazidiphenylmethane, 4,4'-
Diazitosderben, 4,4'-Diazidochalcone, 2,6-di(4'-azidobenzal)cyclohexanone% 2+e-di(s'-7di)"benzal)-
4-methylcyclohexynone, 1-azidopyrene,
Examples include sodium 4,4'-diazidostilbene-22'-disulfonate, 1,5-diazidonaphthalene-3, and sodium fudisulfonate. These azide compounds include those that are soluble in organic solvents and those that are soluble in water, and those that are soluble in organic solvents are usually natural rubber, synthetic dino 1. Pit version 1. It is used by mixing with noyflac resin, etc., while water-soluble ones are usually mixed with polyvinyl alcohol, polyginylpyrrolidone, diacetone acrylamide, methylcellulose, vinyl alcohol-maleic acid copolymer, vinyl alcohol/acrylamide copolymer, etc. It can be used in combination with electrolyte, water-soluble polyvinyl butyral, etc. An example of a polymer having an azide group in the molecule is polyazidovinyl benzoate.

Examples include vinyl polyazidophthalate and polyvinyl benzalacetal. Examples of polymers having a cinnamoyl group in the molecule include 11 vinyl cinnamate; cinnamylidene acetate derivatives of polyvinyl alcohol 1 such as polyvinyl cinnamylidene acetate, polyvinyl cinnamate cinnamylidene acetate, polyvinyl carpethoxymethyl carnomamate cinnamylidene acetate , polyvinyl acetate, cinnamylidene acetate, etc.

In addition to the above, as the photocrosslinkable photosensitive substance, a mixed system of a monomer, oligomer or polymer having an ethylenic bond and a photopolymerization initiator can be used. This kind of monomer.

Specific examples of oligomers or polymers include C: acrylic acid;
Methacrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, 2-hy)'.

Examples include xyethyl methacrylate, ethylene glycol acrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, oligomers thereof, and polymers thereof. Examples of the photoinitiator include conventional ones, such as benzoin, penzoin methyl ether, benzophenone, Michler's ketone, thioxanthone, and anthraquinone sulfonate.

Examples of the fluororesin used in the photosensitive layer of the present invention include polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene-hexafluoropropylene copolymer. Examples include ethylene copolymer, tetrafluoroethylene rubber fluoroalkoxyethylene copolymer, polyfluoroalkyl acrylate, polyfluoroalkyl acrylate, fluoroalkyl acrylate-toluargyl acrylate copolymer, and the like. These 4fQ fats are used in the form of a solution or an emulsion.

The ratio of photosensitive substance and fluororesin in the photosensitive layer is 1:0.2
~10 (weight) is appropriate. When the ratio is less than 1:()2, effects such as oil repellency are small, and when it exceeds 1:10, the resistance of the photosensitive layer to the developer increases, resulting in poor development.

On the other hand, as the thermoplastic resin particles used in the heat-sensitive layer, any thermoplastic resin particles can be used as long as they can be maintained in the form of particles at room temperature in the heat-sensitive layer, but generally the film forming temperature or melting point is 50 to 150 °C thermoplastic resin particles, such as polyvinyl acetate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyethylene, polyacrylic ester, polymethacrylic ester, ethylene-quinyl acetate copolymer, vinyl chloride-vinyl acetate Particles such as copolymers, styrene-acrylic acid copolymers, noserak resins, linear resins, reester resins, ionomer resins, polyisobutylene, polyisoprene, polybutadiene, styrene-butadiene copolymers, chlorinated polyethylene, chlorinated polypropylene, etc. be.

Thermocoagulable proteins include single proteins such as albumin, hemoglobin, globulin, promilan, and glutelin, dried egg whites whose main component is albumin, soybean proteins whose main component is hemoglobin (dried soy milk, concentrated soy protein powder),
Protein-containing substances such as wheat gluten (active wheat protein) whose main components are promilan and glutelin, and rokoshi protein whose main components are promilan, and alkylation, acylation, and esterification of the above-mentioned single proteins and protein-containing substances, Amidation, oxidation.

Examples include chemically modified M elements and others.

Any ammonium salt or amine salt of an insoluble resin that can react with ammonium or amine to form a water-soluble ammonium salt or amine salt can be used. .

Examples of such water-insoluble resins include unsaturated carzeneic acid copolymers such as acrylic acid, crotonic acid, methacrylic acid, isocrotonic acid, maleic acid, fumaric acid, methylmaleic acid, methylfumaric acid, and icconic acid. Copolymer of calzenic acid with a copolymerizable monomer such as vinyl acetate, styrene, α-methylstyrene, acrylic ester, methacrylic ester, ethyl 1/one, propylene, butylene, isopglene, vinyl chloride: 17 sol type or Novolak type phenolic resin; polyvinyl hydroxybenzoate; polyvinyl hydroxybenzal; cellulose acetate hydrogen ν-fucrate; polyhydroxystyrene; shellac; casein; sulfonic acid group-containing monomer; Examples include copolymers, acrylic acid ester-p-toluenesulfonic acid copolymers, and the like.

When these water-insoluble resins are used as ammonium salts or amine salts, they are usually prepared by mixing the resin with aqueous ammonia or amine in a heat-sensitive layer forming solution without isolating the resin as a salt.

As the photothermal converting substance, any substance that can absorb light such as X-rays, ultraviolet rays, visible light, infrared rays, and white light and convert it into heat can be used, such as carin black, carzen graphite, phthalocyanine pigments, Iron powder, graphite powder, iron oxide powder.

Examples include lead oxide, silver blackide, chromium oxide, iron sulfide, and chromium sulfide.

Note that the ratio of the thermoplastic resin particles, thermocoagulable protein and/or ammonium salt or amine salt of the water-insoluble resin to the photothermal converting substance in the heat-sensitive layer is preferably 1:10 to 50 (by weight) 8 degrees. .

In addition, a water-soluble, alkali-soluble or organic solvent-soluble resin binder may be added to the heat-sensitive layer or photosensitive layer, if necessary, up to 90% by weight of the layer weight. Water-soluble or alkali-soluble inders of this type include: pyratine, starch, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, hydroxyethylcellulose, shell alcohol-maleic acid copolymer, vinyl acetate-crotonic acid copolymer, Styrene-maleic acid copolymers, etc., and those soluble in organic solvents include polyvinyl acetate, polystyrene, polyglopyrene, and polyvinylidene chloride.

Examples include homopolymers and copolymers such as polyethylene and polyacrylic esters. In addition, the photosensitive layer may contain a coloring agent (dye or pigment), an IJ agent (for example, p-methoxyphenol), a sensitizer (for example, 5
-Nitroacenaphthene, 2-nitrofluorene, 2-chloro-18-phthaloylnaphthalene% 3-methyl-1
, 3-diaza-1,9-benzanthrone, 2-benzoylmethylene-1-methylnaphthothiazoline, etc.) can be added.

The support used for wood invention is paper laminated with a plastic film (f!!λ is polyethylene s'') film of progylene, polystyrene, etc.).
Synthetic paper, gold discs (e.g. plates of aluminum, zinc, iron, copper, etc.), plastic films (e.g. films of acetic acid trihyllulose, cellulose nitrate, polyethylene terephcrate, polystyrene, polypropylene, polycarbonate, etc.), Vapor deposition, plating or 1
T-layered plastic plate or glass film (
Specific examples of plastics are as mentioned above.

To make a light and heat sensitive recording material invented by wood, for example, g tq
5 properties 1,94 Fat particles (in the form of an emulsion), thermocoagulable proteins and/or ammonium salts or amine salts of water-insoluble resins, photothermal converting substances, and if necessary, insoluble or water-soluble resins are uniformly mixed and dispersed. , this dispersion was applied onto a support and dried at a temperature of 30 to 50°C to form a powder of 0.2 to 50μ,
Preferably, a heat-sensitive layer with a thickness of 1 to 10 μm is provided thereon.

A solution prepared by dissolving or dispersing a photocrosslinkable photosensitive substance, a fluororesin, and if necessary, other water-soluble or water-insoluble resins and additives for the photosensitive layer as described above in a suitable solvent is coated, and at the above-mentioned turbidity. A dry photosensitive layer having a thickness of 0.1 to 50 μm, preferably 0.2 to 15 μm may be provided. In this case, if necessary, an overcoat layer of a water-soluble resin such as gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, hydroxyethylcellulose, etc. is applied on the photosensitive layer for the purpose of preventing the photosensitive layer from becoming sticky, preventing oxidation, protecting the appearance, etc. Further, for the purpose of improving adhesion, a precoat layer of a similar resin can be provided between the support and the heat-sensitive layer.

As described above, in the light and heat sensitive recording material of the present invention, an image is formed by forming a latent image using light and heat (or heat rays) and then developing it with a developer. Sources include mercury lamps, fluorescent lamps, arc lamps, xenon lamps, halogen lamps, and tungsten lamps.

There are infrared lamps, various flash lamps, etc.

As the heat ray source, a flash lamp is preferable, which has a light emission time of about 1/100 second or less and has a high light intensity in the infrared region. It is also possible to use a laser light source.

On the other hand, as the developer, water, alkali aqueous solution, organic solvent, etc. are used depending on the cumulative material in the photosensitive layer or heat-sensitive layer.

Examples of the present invention are shown below. Note that the parts and percentages are both based on electric resistance stitching standards.

Example 1 Carzen black 1 part polyvinyl alkyl (saponification degree 80.5%, 2
0 parts Average degree of polymerization 50 0 10% aqueous solution water
A composition consisting of 17 parts was ultrasonically dispersed, and 100 parts of the composition was
It was coated on a μ-thick polyethylene terephthalate film using a wire parr and dried at 40°C to form a 3 μ-thick heat-sensitive layer.
1 part penzoin isoglobil ether
0.1 part methanol
A composition consisting of 20 parts and 2 parts of polytetranorroethylene fine powder was applied using a wire spar.

A photosensitive layer having a thickness of 5 μm was provided by drying at 40° C.

Next, a negative film original was superimposed on the light-sensitive and heat-sensitive recording material obtained in this way, and it was brought into close contact with the original, and exposed to ultraviolet rays (t/%) for 30 seconds with a 2RW mercury lamp at a distance of 50 CrIL from the original side.
Subsequently, the area was exposed to light for 171,000 seconds using a xenon flash lamp to heat and melt the area. Next, this exposed recording paulownia material was immersed in water and the light-sensitive and heat-sensitive layer was rubbed with absorbent cotton, so that the non-fogged light areas were dissolved and removed by the water, thus forming a clear black positive image. In this case, since the product of the present invention has a wide tolerance range of development conditions, the St point is always 5% at 200 lines.
beautifully reproduced.

On the other hand, as a comparative example, a light and heat sensitive recording material F was prepared in the same manner except that a photosensitive layer not containing fine polytetrafluoroethylene powder was provided, and images were formed in the same manner. was formed, but this one was developed φ
Depending on the temperature, the thin line part may peel off easily (200 lines, 5% halftone dots must be reproduced with great care.

Example 2 A photosensitive liquid having the following composition was coated with a blade on the same heat-sensitive layer as in Example 111, and dried at 40°C to form a photosensitive layer with a thickness of 3 μm, thereby creating a photosensitive material. .

Next, when this recording paulownia material was exposed to light and subjected to 3M and image processing in the same manner as in Example 1, a clear black positive image was formed, and the halftone dots were clearly reproduced down to 200 lines and 5%. It was done.

As a comparative example, sensitization was carried out in the same manner as in this example except that 3 parts of polyacetic acid-dyl emulsion (polysol PS-10 manufactured by Showa Kobunshi Co., Ltd., solid content 50%) was used instead of 10 parts of fluororesin emulsion. Feelings of seagull H1ν record moon ``1 岑・Created,
Exposure, grain removal, and image processing were performed in the same manner, but one image line of the comparative product was easily peeled off during development.

i-j # jU Example 3 Carben black 10 parts Styrene-maleic acid copolymer 1 part 25% aqueous ammonia A composition consisting of 0.5 parts was ultrasonically dispersed to form a uniform dispersion, and this was dispersed into a 100μ thick polyethylene terephthalate. It was coated onto the film using Y-V-72- so that the thickness after drying would be about 5 μm, and dried at 40° C. to form a heat-sensitive layer.

Further, the photosensitive liquid used in Example jFl 2 was applied thereon with a blade and dried at 40° C. to form a photosensitive layer with a thickness of 3 μm, thereby producing a photosensitive and thermosensitive recording material.

Next, when this printing material was subjected to light and development treatment in the same manner as in Example 1, clear dot-colored positive images were formed.

Example 4 Carven black 2 parts dried egg white 2 parts water
A composition consisting of 26 parts was ultrasonically dispersed, and this was applied onto a 100μ thick polyethylene terephthalate film using a wire spar, and dried at 40°C to form a 3μ thick heat-sensitive layer. Furthermore, the photosensitive liquid used in Example 2 was applied with a blade.

A photosensitive layer having a thickness of 3 μm was provided by drying at 40° C. to prepare a light and heat sensitive recording material.

Thereafter, this recording material was exposed to light and developed in the same manner as in Example 1, and a clear black positive image was formed.

Claims (1)

[Claims] 1. On the support ^) selected from the group consisting of thermoplastic resin particles, thermocoagulable proteins, and ammonium salts or amine salts of water-insoluble resins that can react with ammonia or amines to form water-soluble ammonium salts or amine salts. and b) a photothermal converting substance that absorbs light and converts it into heat, and a photosensitive layer containing a photocrosslinkable photosensitive substance as a main component is sequentially provided thereon. A light and heat sensitive recording material comprising: a light and heat sensitive recording material, characterized in that the photosensitive layer further contains a fluororesin;