JPS61198153A - Image recording material - Google Patents

Abstract

PURPOSE:To prevent lowering in the optical density during reduction and the generation of pinholes by forming a recording layer contg. fine particles for providing high light shielding property and a resin binder on a transparent support and a photosensitive layer of photo-cross-linkable polyvinyl alcohol on the recording layer. CONSTITUTION:An image recording layer contg. fine particles for providing high light shielding property, especially fine graphite particles and a resin binder is formed on a transparent support, and a photosensitive layer of photo-cross- linkable polyvinyl alcohol is formed on the recording layer. A transparent film of polyethylene terephthalate or the like is used as the support. It is preferable that the particle size of the fine graphite particles in the recording layer is <=2mum so as to provide high blackening density to the thin film. The optical density of the recording layer is >=0.5 because of the light shielding property. The amount of the resin binder used is 20-100pts.wt. per 100pts.wt. fine particles.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a highly light-shielding image recording material using a photosensitive resin.

[Conventional technology]

Conventionally, in the field of photolithography, silver halide film (1.%e, ?s) has been used for duplicating line drawing originals, creating halftone originals from continuous tone originals, or reversing originals by contact exposure.
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In addition to I÷t)h jN, attempts have also been made to use non-silver salt photosensitive materials from the standpoint of protecting silver resources.

An example of this is a method in which a recording layer containing light-shielding particles such as carbon black and a binder resin is provided, a photopolymerizable layer is further provided thereon, and a halftone-resolved image is reproduced by exposure and development.

[Problem that the invention seeks to solve]

However, in the above case, the recording layer needs to have sufficient light-shielding properties. One way to do this is to increase the content of light-shielding particles in the recording layer, but this is not appropriate because there is a limit depending on the dispersion ability of the binder.

Therefore, in order to improve the light-shielding property, the thickness of the recording layer itself must be increased. However, as the thickness of the recording layer increases, the resolution decreases, which poses a problem in terms of resolution.

An object of the present invention is to improve the above-mentioned drawbacks and to provide an image recording material having significantly higher resolution than conventional non-silver salt image recording materials.

[Means for solving problems]

That is, in the present invention, an image recording layer containing fine particles imparting high light-shielding properties, particularly graphite, and a binder resin is provided on a transparent support, and a photosensitive layer made of photocrosslinkable polyvinyl alcohol is provided thereon. This is an image recording material characterized by the following.

Suitable supports for forming the image recording material of the present invention include transparent films such as polyethylene terephthalate, polyvinyl chloride, polystyrene, polypropylene, polycarbonate, polyethersulfone,
Examples include transparent films such as polyvinylidene chloride and nylon-6.

Fine particles in the recording layer that provide high light-shielding properties include graphite and the like. Graphite can be used alone or in a mixture with carbon black or the like. Graphite is usually used in order to provide a high blackening density in a thin film.
Preferably, particles with a particle size of 0.0 or less are preferable, and more preferably 0.
．． Graphite having a particle size distribution of 50% or more -E for 4 units or less and 25% or more for 0.2 g or less is suitable.

As the binder resin in the recording layer, conventionally used binder resins can be used, such as acrylic resins, cellulose derivatives, phenolic resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and the like.

The optical density of the recording layer is 0.5 or more to provide light-shielding properties,
It is preferably 2.0 or more. If the blackening density is low, the light shielding performance as a negative film or masking film will be poor.

For this reason, the binder resin is 20 to 100 parts by weight, preferably 50 parts by weight, per 1001 parts of fine particles such as graphite.
Used in amounts of parts by weight or less.

Although the thickness of the recording layer depends on the optical polarization, a sufficient density can be obtained even when the thickness is below 1IL. Preferably 0.2~
0.7 body is good.

On the other hand, the thickness of the photosensitive layer in the image recording material of the present invention is 0.
．． The range of 1 to 5 IL is good, and the thickness is preferably 0.3 to 2 P.The photocrosslinkable polyvinyl alcohol used as the photosensitive layer material is 1. For example, dichromate or diazonium salt is added to polyvinyl alcohol as a crosslinking agent. or added with a tetrazonium salt, or a photocrosslinkable group (styrylpyridinium group,
Cinnamic acid residue.

There are polyvinyl alcohol derivatives into which anthracene residues, etc.) have been introduced.

Among them, styrylpyridinium-based photocrosslinkable polyvinyl alcohol is preferably used, and styrylpyridinium-based photocrosslinkable polyvinyl alcohol includes polyvinyl alcohol partially containing photocrosslinkable structural units represented by the following general formula.

[However, A represents the following general formula (I or (■): IX-R1X~ (However, R1 in the formula represents a hydrogen atom, an alkyl group, or an aralkyl group, and a hydroxyl group, a carbamoyl group, an ether bond, an unsaturated bond) , R2 represents a hydrogen atom or a lower alkyl group, X represents an anion, and pus is 0 or 1, and n is a of 1 to 6 a! ! Indicates the number] The light source used to expose the image recording material of the present invention may be any light source that causes the photocrosslinkable polyvinyl alcohol to react, and examples thereof include mercury lamps, xenon lamps, ultraviolet rays, fluorescent lamps, metal halide lamps, and carbon arcs. Examples include lamps, etc.Furthermore, a laser light source having an oscillation range in the ultraviolet region can also be used.

To use the image recording material of the present invention, first, an image mask is placed on the photosensitive layer, and actinic light is irradiated from above to cure the photocrosslinkable polyvinyl alcohol layer in the exposed areas. The exposure time is usually 5 seconds to 2 minutes, depending on the type of light source, type and thickness of the photosensitive layer.

In development, the unexposed portion of the photosensitive layer is first removed with water, and then the recording layer is eluted with the solvent and removed. Use a spray or brush for removal. When the binder resin contained in the recording layer is water-soluble, the recording layer and the photosensitive layer can be developed at the same time with water.

〔Effect of the invention〕

The image recording material according to the present invention has a recording layer having a sufficient optical density and a thin thickness, so that it has high resolution. In addition, since the photosensitive layer has partial strength due to photocrosslinking,
The effect is that there is almost no decrease in optical density or generation of pinholes when power is reduced.

Therefore, the image recording material of the present invention is used not only for image duplication in photolithography as described above, but also as a negative film when making printing plates such as photosensitive resin plates and 28 plates, and as a masking film when making printed wiring boards. You can.

〔Example〕

The present invention will be explained below with reference to examples.

All parts in Reference Examples and Examples represent parts by weight.

Reference Example-1 110 g of N-methyl-γ-picolinium methosulfate and 200 g of terephthalaldehyde were dissolved in 400 ml of methanol under heating, and then 5 rat of piperidine was added and refluxed for 3 hours. After cooling, ethanol was distilled off under reduced pressure, and the mixture was washed with ethyl acetate. The obtained precipitate was dissolved in hot ethanol and ethyl acetate was gradually added to precipitate crystals, which were washed with ethyl acetate and dried.

In this way, 120 g of N-methyl-γ-(p-formylstyryl)pyridinium methosulfate was obtained.

Reference Example-2 50 g of p-hydroxybenzaldehyde and 15 g of sodium hydroxide were dissolved in 100 m/m of ethyl-t'0 sorb, and then 74 g of bromoacetaldehyde dimethyl acetal was added and refluxed for 20 hours. The reaction solution was cooled. After that, benzene was added, and the mixture was washed once with water and then with dilute alkali until the hydroxyaldehyde was removed. This benzene solution was dried over anhydrous potassium carbonate and then distilled to give p-formylphenoxyacetaldehyde dimethyl acetal 3
6g was obtained.

21 g of p-formylphenoxyacetaldehyde dimethiacetal thus obtained and N-methyl-γ-
22 g of picolinium methosulfate was dissolved in 90 m/m of methanol, 4 ml of piperidine was added, and the mixture was refluxed for 4 hours. Thereafter, the reaction solution was cooled, and the precipitated crystals were filtered, thoroughly washed with acetone, dried, and N-methyl-4-(p-
30 g of (2,2-dimethoxyethoxy)styryl)pyridinium methosulfate was obtained.

Reference Example-3 (Preparation of Photocrosslinkable Polyvinyl Alcohol (3)) 9 g of N-methyl-γ-(p-formylstyryl)pyridinium methosulfate obtained in Reference Example-1 and saponification degree of 88
Polyvinyl alcohol 10, mole%, degree of modification 1.700
Heat and dissolve 0g in 900 lj of water, and add 85g to this solution.
After adding 5 g of % phosphoric acid and stirring at 60° C. for 5 hours, the reaction solution was further stirred at room temperature for 1 day and night, and then poured into a large amount of acetone to precipitate the resin.

This was thoroughly washed twice with methanol and dried. The amount of resin obtained was 98 g. The content of stilbazolium groups in this was about 1.2 mol % based on the total amount of polyvinyl alcohol cored structural units.

Reference Example-4 (Preparation of Photocrosslinkable Polyvinyl Alcohol (8)) 30 g of 9N-methyl-γ-(p-formylstyryl)pyridinium methosulfate obtained in Reference Example-1 and saponification degree of 8
8 mol% 1 Polyvinyl alcohol 100 with degree of polymerization 500
g was reacted in the same manner as in Reference Example-3 to obtain 105 g of resin. The content of stilbazolium groups in this is approximately 3.5
It was mol%.

Example 1 The following graphite dispersion (formulation 1) was applied onto a 75-terminated polyester film using a bar code and dried at 80°C. The dry thickness at this time was 0.31 L, and the optical density under ultraviolet light was 3.0. This was used as the recording layer. The photocrosslinkable polyvinyl alcohol aqueous solution (formulation 2) obtained in Reference Example 3 was applied onto this recording layer by dip coating and dried at 60°C. The thickness of this photosensitive layer was 2.

An image mask is placed on this coated film and an ultra-high pressure mercury lamp (2
kW) at a distance of 50 cm for 20 seconds, first, the unexposed part of the photosensitive layer was immersed in water at 40°C for 20 seconds, and the 0-order recording layer that had been eluted and removed was washed with isopropyl alcohol. When the area was developed using a brush, a high-resolution duplicate image was obtained.

Prescription 1 Graphite 100 parts Ethyl cellulose 36 parts Ethyl acetate 1224 parts Water 2400 parts Example 2 On the recording layer coated in Example 1, a photocrosslinkable polyvinyl alcohol (8) aqueous solution obtained in Reference Example-4 (Formulation 3)
was applied by dip coating and dried at 60°C.

The thickness of this photosensitive layer was 1P.

An image mask is placed on this coated film and an ultra-high pressure mercury lamp (2
kW) at a distance of 50 cm for 20 seconds, first, the unexposed part of the photosensitive layer was immersed in water at 40°C for 20 seconds, and the portion of the recording layer from which the photosensitive layer had been removed was brushed with the 0-order isopropyl alcohol that had been eluted and removed. A high-resolution reproduction image was obtained when the image was developed using .

2400 parts of water Example 3 A photocrosslinkable polyvinyl alcohol aqueous solution consisting of the following formulation 4 was applied by dip coating onto the recording layer coated in Example 1, and dried at 60°C. The thickness of this photosensitive layer was IJL.

An image mask is placed on this coated film, and an ultra-high pressure mercury lamp (
After exposure for 40 seconds at a distance of 50 cm using 2kw), first, the unexposed part of the photosensitive layer was immersed in water at 40°C for 20 seconds, and the portion of the recording layer from which the photosensitive layer was removed was eluted with zero-order isopropyl alcohol. When developed using a brush, a high-resolution reproduction image was obtained.

Claims (1)

[Claims] 1. A recording layer containing fine particles imparting high light-shielding properties and a binder resin is provided on a transparent support, and a photosensitive layer made of photocrosslinkable polyvinyl alcohol is provided on top of the recording layer. Characteristic image recording materials. 2. The image recording material according to claim 1, wherein the fine particles are graphite.