JPS58148792A - Photo- and heat-sensitive recording material - Google Patents

Abstract

PURPOSE:To enhance photo sensitivity and mesh-point reproductivity of a photo- and heat-sensitive recording material by adding a substance to convert light to heat and a photo-bridgeable photo-sensitive substance as well as a thermoplastic resin particle to a photo- and heat-sensitive layer. CONSTITUTION:A photo-bridgeable and sensitive substance obtained by mixing a thermoplastic resin particle of a film-forming temperature or melting point of 50-150 deg.C, a light-heat conversion particle to absorb and convert light to heat, a polymer having a diazonium salt or azide compound in its molecule, and polyvinyl alcohol, etc., is provided on a supporter, e.g., plastic film, paper, etc. As the light-heat conversion substance, substances to absorb and convert light to heat, such as carbon black, phthalocyanine pigment, etc., are used. In the photo- sensitive recording material, latent image is formed by means of light and heat and then developed by a developer to form a picture.

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, photo-crosslinking has been used as a photosensitive or heat-sensitive recording material in which a latent image is formed by light such as X-rays, ultraviolet rays, visible light, infrared rays, or the heat generated by absorbing this light, on a support such as paper or film. A washout type photosensitive layer containing a photosensitive agent and a coloring agent such as carmen plaque as the main ingredients (Japanese Patent Laid-open No. 4
No. 8-93325), a heat-sensitive layer containing as active ingredients a binder such as ionomer resin particles, a water-soluble resin, carbon black, and a photothermal converting substance that absorbs light and converts it into heat, such as iron powder, is provided. Things (JP-A-56-14859
No. 0), and one in which thermofusible phenolic resin particles are used in place of the ionomer resin particles in the heat-sensitive recording material (% Patent Application No. 148589/1989) have been proposed.

These photosensitive or heat-sensitive recording materials are exposed to light or heat rays to photo-crosslink the photosensitizer in the exposed areas in the case of photosensitive types, and to crosslink the ionomer resin or phenol in the exposed areas in the case of heat-sensitive types. An image is formed by melting the resin to make the area poorly soluble or insoluble in water, and then dissolving and removing the original water-soluble non-exposed area with water. Because the photosensitivity is low due to the light-shielding effect of The disadvantage is that reproducibility is poor, while heat-sensitive types have severe heat diffusion due to photothermal conversion substances, resulting in thicker images (lower resolution) and poor film strength, oil resistance, and chemical resistance. There were drawbacks such as low

The first object of the present invention is to achieve high light sensitivity and good halftone reproducibility (despite using colorants or photothermal converting substances).
The object of the present invention is to provide a light and heat sensitive recording material which has good resolution, film strength, oil resistance and chemical resistance.

That is, the recording material of the present invention has thermoplastic resin particles on a support, a photothermal converting substance that absorbs light and converts it into heat, and a photocrosslinkable photosensitive substance that absorbs light and undergoes a crosslinking reaction. It is characterized by having a photosensitive and thermosensitive layer.

In this way, the present invention uses a photothermal converting substance and a photocrosslinkable photosensitive substance to compensate for the decrease in photosensitivity caused by the photothermal converting substance, suppress heat diffusion, and improve film strength, oil resistance, and It has improved chemical resistance.

The principle of forming an image (latent image) using the recording material of the present invention is as follows. If the photothermal converting substance absorbs light in the sensitive wavelength range of the photosensitive substance and generates heat, this light can be simply exposed (
From the example, if the photothermal converting substance does not absorb light in the sensitive wavelength range of the photosensitive material or does not generate heat even if absorbed, the photothermal converting substance may be used separately from this light. By sequentially exposing the photosensitive material to light that can be absorbed and generate heat (usually heat rays such as infrared rays), the photosensitive material in the exposed area undergoes a crosslinking reaction, and at the same time, the photothermal converting material generates heat and the coexisting particulate The thermoplastic resin is melted, thereby creating a difference in solubility in a developing solution (water, aqueous alkaline solution, organic solvent, etc.) between the exposed and unexposed areas (the solubility of the exposed area is higher than that of the unexposed area). ).

Next, materials used in the present invention will be explained. First, the photocrosslinkable photosensitive substance may be any substance that absorbs light and undergoes a crosslinking reaction, such as diazonium salts, azide compounds, polymers with an azide group in the molecule, and polymers with a cinnamoyl group in the molecule. etc. are known. Examples of diazonium salts include paraformaldehyde condensates of p-diazodiphenylamine, p-quinonediazide, and p-iminoquinonediazide. Examples of azide compounds include p-phenylenebisazide, p-azidobenzophenone, 4,4-diazidobenzophenone,
゜4'-Diazidodiphenylmethane, 4,4'-diazidostilbene, 4,4-diazidochalcone, 2.6-
Di(4'-azidobenzal)cyclohexanone, 2,
6-di(4'-azidobenzal)-4-methylcyclohexanone, 1-azidopyrene, 4-47-diacidostirpene-2.2'-sodium disulfonate, 1,5
-Sodium diazidonaphthalene-3,7-disulfonate and the like. These azide compounds include those that are soluble in organic solvents and those that are soluble in water. Those that are soluble in organic solvents are usually mixed with natural rubber, synthetic rubber, cyclized rubber, noserak resin, etc.; , water-soluble ones are usually mixed with polyvinyl alcohol, polyvinylpyrrolidone, diacetone acrylamide, methyl cellulose, vinyl alcohol-maleic acid copolymer, vinyl alcohol acrylamide copolymer, water-soluble polyvinyl butyral, etc. be done. Examples of polymers having an azide group in the molecule include polyazidovinylbenzoate, polyazidophthalate vinylino L/, and polyvinylbenzalacetal.

Examples of polymers having a cinnamoyl group in the molecule include polyvinyl cinnamate: cinnamylidene acetate derivatives of polyvinyl alcohol, such as polyvinyl cinnamylidene acetate, polyhinyl cinnamate cinnamylidene acetate, polyvinyl carpethoxymethyl cinnamylidene acetate, and polyvinyl carpethoxymethyl cinnamylidene acetate. Examples include denacetate, vinyl 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 ethylenically unsaturated bond and a photopolymerization initiator can be used. Specific examples of this type of monomer, oligomer or yW IJ -r 6- - include acrylic acid, methacrylic acid, methyl methacrylate, 2-ethylhexyl acrylate, 2
Examples include -hydroxyethyl methacrylate, ethylene glycol acrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, or oligomers or polymers thereof. Examples of the photopolymerization initiator include conventional ones, such as pentuin, benzoin methyl ether, benzophenone, Michler's ketone, thioxanthone, and anthraquinone sulfonate.

As the thermoplastic resin particles, any thermoplastic resin particles can be used as long as they can be maintained in the form of particles at room temperature in the light and heat sensitive layer, but generally those with a film forming temperature or melting point of 50 to 15
Thermoplastic resin particles at 0°C, such as polyvinyl acetate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polyethylene, polyacrylic ester,
Bori methacrylic acid ester, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, styrene acrylic acid copolymer, Tumerac resin, linear polyester resin, ionomer resin, polyisobutylene, polyisoprene, polybutadiene, styrene - There are particles of butadiene copolymer, chlorinated polyethylene, chlorinated polypropylene, etc.

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 Carlo black, CarR graphite, and phthalocyanine. Examples include pigments such as iron powder, graphite powder, iron oxide powder, lead oxide, silver blackide, chromium oxide, iron sulfide, and chromium sulfide.

The ratio of thermoplastic resin particles, photothermal converting material, and photocrosslinkable photosensitive material in the photosensitive and thermosensitive layer is 1:0.1 to 10 by weight.
: About 0.1 to 10 is appropriate.

In addition to the above-mentioned components, the light-sensitive and heat-sensitive layer may contain various water-bathable or hydrophilic resins (including alkali-soluble) or organic solvent-soluble or lipophilic resins as a binder, if necessary.
It can be added up to about 0%.

Supports used in the present invention include paper, paper laminated with a plastic film (for example, a film of polyethylene, polypropylene, polystyrene, etc.), synthetic paper, a metal plate (for example, a plate of aluminum, semi-soft iron, copper, etc.), Plastic films (e.g. films of Flt cellulose, nitrocellulose, polyethylene terephthalate, polystyrene, polypropylene, polycarbonate, etc.),
Examples include plastic plates or plastic films (specific examples of plastics are as described above) on which metals such as those described above are vapor-deposited, plated, or laminated.

To make the photosensitive and thermosensitive recording material of the present invention, for example, a thermoplastic resin emulsion, a photocrosslinkable photosensitive material, a photothermal converting material, and a binder if necessary are mixed, and after uniformly dispersing by stirring and isobaric ultrasonic dispersion, The obtained dispersion is coated so that the thickness after drying is 1 to 50 μm, preferably 1 to 15 μm = 9 = cloth, and dried at a temperature of 30 to 50°C to form a photosensitive and heat sensitive layer. good. In this case, if necessary, a precoat layer made of a suitable resin may be further provided between the support and the photosensitive heat sensitive layer, and an overcoat layer made of a suitable resin may be provided on the photosensitive heat sensitive layer.

As mentioned 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. In this case, the light source used is Or as a heat ray source, mercury lamp, fluorescent lamp, arc lamp,
There are xenon lamps, halogen lamps, tungsten lamps, infrared lamps, various flash lamps, etc., but as a heat ray source, the emission time is about 4 degrees. It is preferable to use a flash lamp that takes less than a second 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 a developer, water, aqueous alkaline solution, organic solvent, etc. are used depending on the material in the light and heat sensitive layer. The image area of the recording material after development can be transferred to a suitable image-receiving sheet even if it remains wet or dry. Further, by utilizing the difference in hydrophilicity or lipophilicity between the image area and the non-image area, a plurality of copies can be obtained by using the developed recording material as a lithographic printing plate.

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

Example 1 A composition consisting of 1.0 part of Car 27 Black was ultrasonically dispersed and spread on a 100 μm thick polyethylene phthalate film using a wire. - to give a weight after drying of about 41/m'', and dried at 40°C to form a light and heat sensitive layer.

Next, a negative film original was superimposed on the light-sensitive and heat-sensitive recording material obtained in this way and vacuum-adhered, and exposed to ultraviolet light for 30 seconds using a 2KW mercury lamp at a distance of 50 crn from the original, and then exposed to ultraviolet light for 71,000 seconds using a xenon flash lamp. The part was heated and melted under white light for a second. Next, this exposed recording material was immersed in water and the light 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.

On the other hand, as a comparative example, a light- and heat-sensitive recording material was prepared by pressing in the same manner except that Sepian A312 was not used. Thereafter, similar exposure and development operations were repeated on this recording material, but the fine line portions of the image peeled off and a satisfactory image could not be obtained.

Example 2 A mixture consisting of 1 part Carmen Black and 40 parts methyl cellosolve was dispersed in a l-lumil for 1 hour, and then dried using a wire knot on a polyethylene terephthalate film with a thickness of 100 μm, so that the weight after drying was about 41 tons/L. m'' and dried at 50°C to form a photosensitive and heat sensitive layer.

Next, the light and heat sensitive recording material thus obtained was subjected to the same exposure and development operations as in Example 1, and a clear black positive image was formed.

On the other hand, as a comparative example, a light and heat sensitive recording material was prepared in the same manner except for Polymis) A-12.

13- With this product, thin line portions peeled off using the same exposure and development method, and a clear image could not be formed.

Example 3 2.0 parts of Carmen Black 120 parts of polyester acrylate (Aronix M8060 manufactured by Toagosei Co., Ltd.), 8 parts of a 25% aqueous solution of a nonionic surfactant (Emulgen 935 manufactured by Kao Atlas Co., Ltd.) and 72 parts of water were emulsified and dispersed. A mixture consisting of 2.5 parts of the water-related dispersion liquid was dispersed by ultrasonic waves, and this was placed on a 95 μ thick synthetic paper (Copo FP-95 manufactured by Tamago Yuka Synthetic Paper Co., Ltd.) so that the weight after drying was approximately 417 m''. 14- Next, the light and heat sensitive recording material thus obtained was subjected to the same exposure and development operations as in Example 1, and a clear black positive image was formed. When this recording material was scanned and exposed to UV argon laser light with an output of IKW and then developed, a clear black image was formed only in the scanned area.

On the other hand, as a comparative example, a light and heat sensitive recording material was prepared in the same manner except that Copolene Latex L-6000 was removed. With this product, thin line portions peeled off using the same exposure and development method, and a clear image could not be formed.

15-

Claims (1)

[Claims] 1. On a support, there is a photosensitive and thermosensitive layer mainly composed of thermoplastic resin particles, a photothermal converting material that absorbs light and converts it into heat, and a photocrosslinkable photosensitive material that absorbs light and undergoes a crosslinking reaction. Light and heat sensitive recording material.