JPS60101088A - Photosensitive heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To attain to enhance resolving power and the strength, oil resistance and chemical resistance of a film, by successively providing a heat-sensitive layer based on a light-heat converting substance and a water-insoluble thermoplastic resin particle and a photosensitive layer based on a specific diazo compound and an epoxy compound on a support. CONSTITUTION:As a light-heat converting substance, a substance capable of converting light to heat upon the absorption of heat is used and, as a water-insoluble thermoplastic resin or a water-soluble thermoplastic resin becoming substantially water- insoluble by heat, one capable of being held as a particle at ambient temp in the heat- sensitive layer is used. On the other hand, as the photocrosslinkable photosensitive substance of a photosensitive layer, an epoxy compound consisting of a diazo compound for releasing Lewis acid and diglycidyl ether of glycol or polyglycidyl ether of polyol is used. By using the above mentioned components, a thermoplastic resin emulsion and the light-heat converting substance are uniformly dispersed while the resulting dispersion is applied to a support and dried to form the heat-sensitive layer and a solution, which is prepared by mixing the diazo compound and the epoxy compound while dissolving or dispersing the resulting mixture in a solvent, is applied to said heat- sensitive layer and dried to provide the photosensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a light and heat sensitive recording material in which a latent image formed with light and heat can be developed with water.

Prior Art Conventionally, ionomers have been used as photosensitive or heat-sensitive recording materials on which a latent image is formed by light such as ultraviolet light, visible light, infrared light, or white light, or by the heat generated by absorbing this light, on a support such as paper or film. A heat-sensitive layer containing a photothermal converting substance such as resin particles, water-soluble resin, carbon black, and iron powder that absorbs light and converts it into heat as an active ingredient (JP-A-56-1
No. 48590), the recording material in which phenolic resin particles are used instead of ionomer resin particles (
JP-A-56-148589), a colored layer containing alcohol-soluble polyamide and a coloring agent as main components on a support, and a photosensitive layer containing an alcohol-soluble photocrosslinkable photosensitive material (photoresist) as a main component thereon. (Utility Model Application Publication No. 55-164647) is known. Among these, the heat-sensitive type uses infrared rays for image exposure.
An image is formed by melting or thermally crosslinking the ionomer resin or phenolic resin in the exposed area to make this area poorly soluble or insoluble in water, and then dissolving and removing the original water-soluble non-exposed area in a developer (water). In addition, the photosensitive type is image-wise exposed to ultraviolet rays, and the photosensitive material in the exposed area is photo-crosslinked, and as with the heat-sensitive type, a developer (in this case, a developer is applied between the exposed area and the unexposed area) After creating a solubility difference in (alcohol), the non-exposed areas are dissolved and removed in a developer, thereby forming an image. However, in the case of heat-sensitive type, infrared irradiation and heat diffusion due to photothermal converting substances occur, resulting in drawbacks such as inability to obtain high-resolution images and low strength, oil resistance, and chemical resistance of the film, that is, the heat-sensitive layer. On the other hand, in the case of a photosensitive type, the colored layer is also added to the developer, so during development, the colored layer in the image area is side-etched, resulting in poor reproducibility of points and lines (hereinafter referred to as halftone dots). It had the disadvantage of suffering from P) current status.

Object The object of the present invention is to provide a light and heat sensitive recording material which can form high-resolution images with excellent halftone dot reproducibility, has excellent film strength, oil resistance and chemical resistance, and is highly sensitive.

Structure The light- and heat-sensitive recording material of the present invention contains on a support a) a photothermal converting substance that absorbs light and converts it into heat, and b) water-insoluble thermoplastic resin particles or a water-soluble thermoplastic resin that becomes substantially water-insoluble when heated. A heat-sensitive layer containing a plastic resin as a main component, and a) a diazo compound that releases a silicate acid when exposed to light as a photo-crosslinkable photosensitive substance, and b) an epoxy compound such as diglycidyl ether of glycol or polyglycidyl ether of polyol. It is formed by sequentially providing a photosensitive layer as a main component.

In this way, the recording material of the present invention combines a conventional heat-sensitive layer and a photosensitive layer containing a specific mixed photocrosslinkable photosensitive material, thereby mutually compensating for the defects inherent in each layer, and As will be explained in the following image forming method, the sensitivity and resolution are further improved.

The principle of forming an image (latent image) using the recording material of the present 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. If the material does not absorb the light, the photosensitive material in the exposed area of the photosensitive layer can be removed by sequentially exposing it to light (usually heat rays such as infrared rays) that the photothermal converting material can absorb, in addition to this light. At the same time, the photothermal converting substance in the underlying heat-sensitive layer is caused to generate heat by light absorption, melting the coexisting thermoplastic resin particles, and thus forming a bond between the exposed and non-exposed areas of the photosensitive layer and the heat-sensitive layer. This creates a difference in solubility in the developer (water) between the two. When the photothermal converting substance in the heat-sensitive layer generates heat due to light absorption, this heat substantially renders the thermolabile resin in the heat-sensitive layer water-insoluble, if it is water-soluble. By promoting the crosslinking reaction of the photocrosslinkable photosensitive material in the upper photosensitive layer and efficiently producing a developer (water) resistant resist, sensitivity and resolution are dramatically improved.

Next, materials used in the present invention will be explained. First, as the photothermal converting substance used in the heat-sensitive layer, 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 carbon black, carbon graphite, etc. , phthalocyanine pigments, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, chromium sulfide, and the like.

In addition, as the water-insoluble thermoplastic resin or the water-soluble thermoplastic resin that becomes substantially water-insoluble by heat, any thermoplastic resin particles that can be maintained in the form of particles at room temperature in the heat-sensitive layer can be used. Film temperature or melting point is 50-1
50'c, thermoplastic resin particles such as polyvinyl acetate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyethylene, polyacrylic ester, polymethacrylic ester, ethylene-vinyl acetate copolymer, vinyl chloride -Vinyl acetate copolymer, styrene acrylic acid copolymer, novolak resin, linear polyester resin, ionomer resin, polyisobutylene, polyisoprene, polybutadiene, stycine-butadiene copolymer, chlorinated polyethylene, chlorinated polypropylene, etc. Water-insoluble particles or unsaturated carboxylic acid copolymers such as acrylic acid, crotonic acid, methacrylic acid, incrotonic acid, maleic acid, fumaric acid, methylmaleic acid, methylfumaric acid, itaconic acid, etc. Copolymers with copolymerizable monomers such as vinyl acetate, styrene, α-methylstyrene, acrylic esters, methacrylic esters, ethylene, propylene, styrene, isobutylene, vinyl chloride; resol type or novolac type phenolic Brl; Ho! J vinyl hydroxybenzoate; polyvinyl hydroxybenzene; cellulose acetate hydrogen phthalate; polyhydroxystyrene; shellac; casein; sulfonic acid group-containing monomer copolymers, such as styrene to p-)luenesulfonic acid copolymers, acrylic acid esters ~p-) Ammonium salt or amine salt such as luenesulfonic acid copolymer; degree of saponification 7
Examples include water-soluble particles such as polyvinyl alcohol containing 5 mol% or more.

Note that the ratio of the water-insoluble thermoplastic resin particles or the water-soluble thermoplastic resin that becomes water-insoluble by heat and the photothermal convertible substance in the heat-sensitive layer is approximately 1:0.1 to 10 (by weight). is.

In addition, a water-soluble, alkali-soluble or organic solvent-soluble resin binder may be added to the heat-sensitive layer in an amount up to about 90% by weight of the layer weight, if necessary. Examples of water-soluble or alkali-soluble binders include gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, hydroxyethylcellulose, vinyl alcohol-maleic acid copolymer, vinyl acetate-crotonic acid copolymer, and styrene-maleic binder. Examples of acid copolymers and organic solvent-soluble ones include homopolymers and mineral copolymers such as polyvinyl acetate, polystyrene, polypropylene, polyvinylidene chloride, polyethylene, and polyacrylic acid ester.

These are used in the form of an emulsion during layer formation.

On the other hand, a diazo compound used as a photocrosslinkable photosensitive material in a photosensitive layer releases a Lewis acid upon exposure to light, and is represented by the following general formula.

(Ar-N=N)a[M×b+a)-a(However, Mi
jFa, Sn, Sb, B, P, As or B1. X represents F or C6, Ar represents an aromatic ring, and a, b/Ii integer. ) A specific example is the following passage.

2. 4-dichlorobenzenediazonium FeC1゜p
-Nitrobenzenediazonium FeC114p-morpholinobenzenediazonium FeC1゜2, +-dichlorobenzenediazonium 5nC16p-nitrobenzenediazonium S n Claz, a-dichlorobenzenediazonium BF.

p-chlorobenzenediazonium PF.

z,4-dichlorobenzenediazonium PF.

2.4,6-)IJ dichlorobenzenediazonium F.

p-diazodiphenylamine PF.

1)-=) Robenzendiazonium PF.

0-nitrobenzenediazonium PF.

4-nitro-〇-toluenediazonium PF.

p-N-morpholinobenzenediazonium BF.

2-nitro-P-)luenediazonium PF6 rhonitro-2,4-xylenediazonium PF.

p-morpholinobenzenediazonium PF.

Nyldiazonium PF.

2. 4', 5-}ethoxy4-biphenyldiazonium PF, 4-(dimetelamino)-1-naphthalenediazonium PF, p-nitrobenzenediazonium AsF6p-mo)
Iz holinobenzenediazonium AsF62,5-dichlorobenzenediazonium SbF, p-nitrobenzene siasoni+7 SbF, p-morpholinobenzenediazonium SbF62,4-dichlorobenzenediazonium fZ bbc462,4-dichlorobenzenediazonium BiCl60-nitrobenzene Diazonium BiC
1. Specific examples of epoxy compounds made of diglycidyl ether of glycol or polyglycidyl ether of polyol, which are also used as photosensitive materials for photocrosslinking, are as follows.

Ethylene glycol diglycidyl ether diethylene glycol diglycidyl ether triethylene glycol diglycidyl ether polyethylene glycol diglycidyl ether (average molecular weight approximately 500) propylene glycol diglycidyl ether dipropylene glycol diglycidyl ether polypropylene glycol diglycidyl ether (average molecular weight approximately 200)
) Neopentyl glycol diglycidyl ether Clycerol diglycidyl ether Glycerol triglycidyl ether Trimethylol propane siglycidyl ether Trimethylol propane triglycidyl ether Noregi glycerol polyglycidyl ether Sorbitol Polyglycidyl ether The mixing ratio of the diazo compound and the eboxy compound is l:
o. l-100 (weight), preferably about l:1 to 20 is appropriate.

In addition, the following resins or compounds can be added to the photosensitive layer in order to adjust the water resistance, flexibility, scratch resistance, etc. of the image. For example, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, ethylcellulose, polyvinyl acetal, polyvinyl petral,
Examples include polyvinyl acetate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylate, polymethacrylate, diglycidyl ether of bisphenol A, polyglycidyl ether of cresol novolak resin, polyglycidyl ether of phenol novolak resin, and the like. It is generally appropriate to use about 0.1 to 1 part by weight per 1 part by weight of the epoxy compound. Supports used in the present invention include paper, paper laminated with a plastic film (e.g., film of polyethylene, polypropylene, polystyrene, etc.), synthetic paper, metal plate (e.g., plate of aluminum, zinc, iron, copper, etc.), plastic Films (e.g. cellulose acetate, cellulose nitrate, polyethylene terephthalate, polystyrene, polypropylene,
A plastic plate or a plastic film on which metals such as those mentioned above are vapor-deposited, plated, or laminated (specific examples of plastics are mentioned above), etc. may be mentioned.

To make the photosensitive and thermosensitive recording material of the present invention, for example, a thermoplastic resin emulsion, a photothermal converting substance, and a binder if necessary are mixed, and after uniformly dispersing by stirring, ultrasonic dispersion, etc., this dispersion is Sade 0. After coating to a thickness of 1 to 50μ, preferably 1 to 10μ and drying at a temperature of 30 to 50°C to form a heat-sensitive layer, a diazo compound, an epoxy compound, and if necessary, a resin and a colorant are added. , filler, etc., dissolved or dispersed in an appropriate solvent, and the thickness after drying is 0.1 to 50 μm, preferably 0.2 to 50 μm.
The photosensitive layer may be formed by coating the film to a thickness of 15 μm and drying at a temperature of 30 to 50° C. In this case, if necessary, an overcoat layer of water-soluble resin such as gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, hydroxyethylcellulose, etc. may be added on the photosensitive layer for the purpose of preventing adhesion of the photosensitive layer, protecting the surface, etc., and improving adhesion. For this purpose, a similar precoat layer of resin can be provided between the support and the colored 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, tungsten lamps,
There are infrared lamps, various flash lamps, etc.

In addition, as a heat ray source, the emission time is about 1/100 second or less,
In addition, a flash lamp with high light intensity in the infrared region is preferable. It is also possible to use a laser light source. Note that water is used as the developer as described above.

Effects As described above, the recording material of the present invention eliminates all the drawbacks of conventional heat-sensitive layers and photosensitive layers by combining a conventional heat-sensitive layer and a photosensitive layer containing a specific mixed photocrosslinkable photosensitive material. death,
In particular, sensitivity, resolution (halftone dot reproducibility), and developability can be improved.

Examples of the present invention are shown below. Note that both parts and percentages are based on weight.

Example 1 Carbon black 1 part 55% emulsion of vinyl acetate-acrylic acid ester copolymer (Sevian A-512 manufactured by Daicel) 2 parts 10% polyvinyl alcohol (saponification degree 80.5%, average polymerization degree 500) Aqueous solution: 20 parts Water: 17 parts This composition was dispersed ultrasonically, applied onto a 100μ thick polyethylene terephthalate film using a wire bar, dried at 40°C, and then heated to a 3μ thick film.
After forming the eel, add ethyl alcohol 50 parts p-morpholinobenzenediazonium P F6 salt 1.0
A composition consisting of 0.5 parts of ethyl cellulose was applied using a wire bar and heated at 40°C.
A photosensitive layer having a thickness of 1 μm was provided by drying.

Next, a negative film original was superimposed on the thus obtained light- and heat-sensitive recording material and vacuum-adhered, and the original was exposed to light from a xenon flash lamp for 1/1000 seconds to heat and melt that part. Next, this exposed record strip was immersed in water and the photosensitive and heat sensitive layer was rubbed with absorbent cotton, so that the unexposed areas were dissolved and removed by the water, thus forming a clear black positive image.

Example 2 Carbon black 2 parts 10% aqueous solution of polyvinyl alcohol (saponification degree 99 mol%, average degree of polymerization 1700) 10 parts Water 20 parts A composition of 2 parts water was dispersed in a ball mill for 5 hours to form a heat-sensitive layer forming liquid. Manufactured. On the other hand, as a photosensitive layer composition of the present invention, 1 part of BF, salt of p-diasocyphenylamine-formaldehyde condensate, 30 parts of phenol borac type EPN-1138) methyl cellosolve, and as a comparative photosensitive layer composition, p-diazo BF of diphenylamine-formaldehyde condensate, salt, 2 parts, epoxy resin (same as above), 2 parts, 30 parts of methyl celonorub were prepared, and these compositions were each dissolved to prepare a photosensitive layer forming liquid. Next, the heat-sensitive layer forming liquid was applied onto a 100μ thick polyester film using a wire bar, and
After drying at °C to form a heat-sensitive layer with a thickness of about 3 μm, each of the photosensitive layer forming liquids was applied thereon using a wire bar,
A photosensitive layer having a thickness of about 1 μm was provided by drying at 50° C.

Next, a negative film original was placed in close contact with each of the recording materials obtained in this way, and exposed from the original side using a xenon flash light source.Then, the film was developed by immersing it in water and rubbing the exposed surface with absorbent cotton. The results were obtained.

As described above, the products of the present invention have higher sensitivity and are easier to develop than comparative products, and have excellent halftone dot reproducibility.

Patent applicant Rico Co., Ltd.

Claims (1)

[Claims] 1. On a support, a) a photothermal converting substance that absorbs light and converts it into heat, and b) water-insoluble thermoplastic resin particles or a water-soluble thermoplastic resin that becomes substantially water-insoluble by heat, as the main components. and a photosensitive layer containing as a photocrosslinkable photosensitive material a) a diazo compound moiety that releases a Lewis acid when exposed to light, and b) an epoxy compound consisting of diglycidyl ether of glycol or polyglycidyl ether of polyol as a main component. A light- and heat-sensitive recording material comprising sequentially provided with and.