JPS60191238A - Image duplication material and its manufacture - Google Patents

Abstract

PURPOSE:To obtain an image duplicating material superior in scratch resistance by incorporating a specified silane coupling agent, a silicone oil or silicone grease in a photosensitive resin layer, and allowing it to migrate to the surface of this layer. CONSTITUTION:An intended image duplicating material is obtained by preparing an agent for enhancing scratch resistance selected from a silane coupling agent and a silicone oil and grease represented by the formula (l, m, are each 0 or 1; n is 1-3; R1 is 1-3C alkylene; R2 is 1-3C alkyl, acetyl, or the like; and Y is 1-18C alkyl, vinyl, or the like), such as vinyltriacetoxysilane, adding this agent to a photosensitive resin compsn., coating a support with this compsn. to form a photosensitive resin layer, allowing this agent to migrate to the surface of this layer, and when needed, forming a protective layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to image reproduction materials capable of providing images with improved surface scratch resistance.

Image duplicating materials have traditionally been used in many fields such as information recording, printed circuit board production, plate making, and printing, and are required to meet the basic performance requirements (resolution, photosensitivity, etc.) for each application. However, a major dissatisfaction for users is that when used under various conditions, scratches occur on the surface of the formed image, which not only requires the entire process to be redone, but also causes a huge amount of damage. There is a problem of loss of time and materials. Such lack of scratch resistance on the image surface is often found in image carriers made of polymers, ie, in image duplicating materials that utilize photosensitive resins.

Image duplication materials that use photosensitive resins have high light sensitivity resolution,
Since it is very advantageous in terms of safety and cost, resolving the lack of scratch resistance has been a major concern for a long time, and at present, techniques such as after-baking and resin coating after image formation are insufficient. Although the situation has been overcome, there is no solution to this problem that essentially goes back to the structure of the image reproduction material.

In response to this situation, the present inventors have conducted extensive research into the fine structure of image duplicating materials that can significantly improve the scratch resistance of formed images, and have finally completed the present invention.

That is, the present invention provides an image duplicating material having at least a photosensitive resin layer, a scratch-resistant layer and a protective layer on a support, wherein the scratch-resistant layer has the general formula Y(-0+t
An image duplicating material characterized in that it contains one or more selected from silicone oil and silicone grease.

In the method of producing an image duplicating material by laminating or coating a protective layer, the photosensitive resin m6 has the general formula Y+C++
t(-Rt +m81 (-OR2). After containing in advance one or more selected from a pulling agent, silicone oil, and silicone grease, it is applied onto the surface of the photosensitive resin layer. A method for producing an image reproduction material characterized by transferring.

Suitable supports for use in the image reproduction material in the present invention include glass plates, plastic films, metal plates, papers and the like. Examples of plastic films include films of polyester, polypropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, cellulose acetate, and the like. In particular, a biaxially stretched sheet polyester film is preferred since it has excellent dimensional stability and transparency. Although there is no strict limit to the thickness of the support, a thickness of 75 to 125 μm is appropriate.

In the present invention, the effect is observed even when the support is in direct contact with the photosensitive resin layer, and in particular, the support is impregnated with an adhesive compound that can improve the adhesive strength to the photosensitive resin layer. Although this is true in some cases, a generally preferred configuration is one that has a subbing layer between the support and the photosensitive resin layer. The subbing layer can be a thin layer of polymeric material or a thin layer of metal or metal compound.

Preferred polymer compound thin layers include, for example, polyacrylate, polyvinylidene chloride/acrytetranitrile/itaconic acid copolymer, hinyl chloride/hinyl acetate/maleic anhydride copolymer, and terephthalic acid/isophthalic acid/glycol copolymer. Examples include coalescence and thin films of polymeric substances such as isocyanate compounds. Layer thickness is usually 0.2~
It is 2μ.

Further, metals or metal compounds of the metal or metal compound layer that are preferable as the subbing layer include aluminum, boronium, iron, magnesium, silicon, titanium, cobalt, copper, indium, iridium, lead, manganese, molybdenum, nickel, palladium, Examples include platinum, pdium, selenium, silver, tanker, tin, tungsten, vanadium, zinc, zirconium, etc., and alloys, oxides, nitrides, borides, carbides, sulfides, and salts of the above metals, such as Examples include aluminum oxide, magnesium fluoride, titanium oxide, silicon oxide, and aluminum-zinc alloys. Among these metals or metal compounds, aluminum or its alloys or compounds are most preferred in terms of cost and high etching rate in aqueous solvents. Methods for providing a thin layer of metal or metal compound on a support include plating, vacuum deposition, sputtering, ionized electrostatic plating, and the like. The thickness of the metal or metal compound varies depending on the type of metal or metal compound, but is usually 100 to 300.
It is 600x.

The photosensitive resin in the present invention refers to a resin composition that undergoes rapid physicochemical changes upon irradiation with actinic rays. Photoreactions commonly used for this purpose include photolytic insolubilization, photolytic solubilization, and photolytic insolubilization. Although reaction, photocrosslinking reaction, or photopolymerization reaction is typical, free radical coloring reaction, diazo coloring reaction, diazo foaming reaction, etc. are also used. The present invention is applicable and effective to photosensitive resins using any of these types of photoreactions.

Typical examples of photosensitive resins that utilize the photolytic insolubilization reaction include condensation products of 4-diazo-1,1'-diphenylamine sulfate and paraformaldehyde,
A typical example of a photosensitive resin that utilizes a photolytic solubilization reaction is a mixture of a quinone diazide, such as a naphthalene-1,2-quinone azide derivative, and a novolac. It is well known that the photocrosslinkable photosensitive resin includes a cinnamoyl group or a cinnamylidene group in its polymer structure. The photopolymerizable photosensitive resin is mainly composed of a monomer or oligomer-1 having an ethylenically unsaturated bond as a polymeric binder and a photoinitiator, and is used as a photosensitive resin layer and various image duplicating materials. Many examples can be seen in . These various types of photosensitive resin layers may be visually transparent, or may contain a coloring agent such as dye 1 pigment or a light blocking agent, and the effects of the present invention will still be achieved. It is possible to realize this.

In the present invention, the most effective product is an image-formed product consisting of an upper layer portion in which the image forming area is hardened and an unhardened lower layer portion by imagewise exposing the image duplicating material and removing the easily soluble portion. It is an image reproduction material having a photosensitive resin layer which gives Since image formations obtained from such image duplicating materials have an uncured lower layer, the lower layer is likely to be destroyed by scratches on the surface, and this invention can be put to practical use for the first time. It is.

The photosensitive resin layer constituting the image duplicating material is photopolymerizable and consists of a photoinitiator, a monomer, and a binder, and also contains a colorant or a light shielding agent that can act as an actinic ray absorber for the photosensitive resin. Ingredients and other necessary stabilizers, plasticizers,
Contains surfactants, etc.

The composition of each of the photosensitive resin layers will be described in detail below.

a) Photoinitiator A photoinitiator has the ability to initiate a polymerization reaction or a crosslinking reaction with actinic rays, and is used alone or in combination with other compounds. Examples of typical compounds include benzyl, benzophenone, Michler's ketone, 4.4'
-benzophenone derivatives such as bis(diethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone.

Aromatic ketones such as anthraquinone, 2-tetraluanthraquinone, 2-ethyl anthraquinone, 1-chloroanthraquinone, aenanthraquinone, benzoin, benzoin alkyl ethers, benzoin derivatives such as α-methylbenzoin, benzyl・Dimethyl ketal, polynuclear monones, combination systems of 2,4,5-triarylimidazole dimer and free radical generator, etc. Furthermore, the sensitivity can be further improved by adding a sensitizer or a sensitizing dye. In addition, 2, 4.
As the 5-triarylimidazole dimer, 2-(
0-methoxyphenyl) -a,S-diphenylimi#
"/-ru dimer, 2-(0-lytetralphenyl)-4,5
- diphenylimidazole dimer, 2-(P-methylmerocaptophenyl) - triphenylimidazole dimer such as 4,5-diphenylimidazole dimer, 2-
(l-naphthyl) -a, 5-diphenylimidazole dimer, 2-(9-anthryl) -4,5-diphenylimidazole 2I 1 body, 2-(2-methoxy-1-naphthyl) -4,5-diphenyl imidazole dimer,
2-(2-methoxy1-naphthyl), 4.5-
(0-methoxyphenyl)imidazole dimer, 2-(
Polycyclic aryl-4,5-diphenylimidazole dimers such as 2-ri[1-i-+7't-l)-4,5-diphenylimidazole dimer can be mentioned.

2.4.5-) Free radical generators used in combination with the aryl imidazole dimer include p, p'-
p-aminophenyl ketone compounds such as bis(dimethylamino)benzophenone, leucomalachite green,
Glue icotriphenylmethane dyes such as leuco crystal violet, cyclic diketone compounds such as 2,4-diethyl-1,3-shift-tetrabutanedione, thioketone compounds such as 4,4-bis(dimethylamino)thiobenzophenone, 2-mercaptobenzo Examples include mercaptan compounds such as thiazole, N-phenylglycine, dimedone, 7-ethylamino-4-methylcoumarin, and the like.

Sensitizers or sensitizing agents include xanthine, acridine, thiazine, and cyanine! dyes are effective.

b) Monomers The monomers used may have one or more polymerizable double bonds. Examples of such compounds include alkyl acrylates or alkyl methacrylates such as hexyl acrylate/hexyl methacrylate, Schiff ν hexyl acrylate, cyclohexylated methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate; hydroxyalkyl acrylate,
Alkyl ether acrylates or methacrylates such as hydroxyalkyl methacrylate, NN-dialkylaminoalkyl acrylate or methacrylates, methoxyethyl acrylate, ethoxyethyl methacrylate, tetragenated alkyl acrylate or methacrylate, alkyl acrylic or methacrylate Acrylates or methacrylates of polyalkyl ethers such as acrylamides, hydroxyalkyl acrylates or methacrylates, diethylene glycol diacrylate or methacrylate, triethylene glycol diacrylate or methacrylate, ethylene glycol diacrylate or dimethacrylate, glycerin, Trimethi four bread,
Acrylates or methacrylates of polyhydric alcohols such as pentaerythritol, reaction products of acrylic acid, methacrylic acid, glycidyl acrylate or methacrylate with active hydrogen-containing substances, reaction products of glycysyl compounds and acrylic acid or methacrylic acid, Examples include a condensate of an N-methyl compound and a urea compound, and a reaction product of a polyisocyanate compound and dorxyalkyl acrylate or methacrylate. The monomer used is 1
The monomer to be used must be selected depending on the type of binder, the ratio of monomers, the type and amount of photoinitiator, the type and amount of actinic ray absorbing compound, etc., without being limited to the type. It is determined based on compatibility, film-forming properties, stability, photosensitivity, etc. If the monomer used has a low boiling point, it will decrease during or after film formation, so a higher boiling point is desirable.

C) Binder The binder is an organic polymer that is soluble in a solvent and is solid at temperatures below 50° C., and must be compatible with a polymerizable monomer. The binder may or may not be thermoplastic, but it must have film-forming ability, and in particular it must have film-forming ability even when monomers, photoinitiators, and actinic light absorbers are added. be.

Examples of such binders include cellulose esters and ethers and their coexisting derivatives (cellulose ethyl ether, cellulose acetate, carboxymethyl cellulose, cellulose acetate succinate, cellulose methyl ether phthalate, cellulose methyl ether succinate, etc.); Polyalkyl ethers, polyesters, polyamides, polyvinyl esters and their copolymers, phenolic resins, polyvinylidene compounds, polyvinyl alcohols, gelatin and its derivatives, polyvinyl butyral, polyacrylamide, polyvinylpyridone, polystyrene, chlorinated Rubber, polyethyleneimine, etc.

In particular, in order to be able to develop with an aqueous developer, it is necessary that the binder itself be dissolved or dispersed in the aqueous developer. Examples of such polymers include polyvinyl alcohol, polyacrylamide, sulfone groups, acid-quaternized units of tertiary nitrogen-containing polymers, polymers containing carboxyl groups, polyvinylpyrrolidone, polyethyleneimine, and the like.

Examples of binders soluble in acidic or alkaline aqueous solutions include carboxyl group-containing cellulose derivatives such as carboxymethyl cellulose, cellulose methyl ether phthalate, and cellulose ethyl ether succinate, methacrylic acid, acrylic acid, maleic acid, itaconic acid, and phosphoric acid. Examples include copolymers of tonne and vinyl monomers, polyesters containing tertiary nitrogen groups, polyamides, and polyethers.

Note that the main chain or side chain of the binder may contain a polymerizable unsaturated double bond group.

d) Actinic Ray Absorber By adding a compound effective in absorbing actinic radiation to the photoinitiator, an image that is opaque to actinic radiation is formed. By increasing the absorption of actinic rays, in the image portion exposed through the transparent portion of the mask, only the upper layer undergoes a curing reaction, while the lower layer remains uncured. As described above, if the uncured lower layer portion can be maintained, the force reducing property, which is an advantageous characteristic for use as a plate-making film, can be maintained. On the other hand, if the amount of actinic ray absorption is small, the lower layer will be hardened during side exposure, making it impossible to reduce the force later. In addition, if the active light me yield is too large,
Only the very thin upper layer can be cured, resulting in poor resist effectiveness and reduced photosensitivity. The most preferable photosensitive layer has an actinic ray absorbance of 1.5 to 4.

Actinic light absorbers used include ultraviolet absorbers, ultraviolet absorbing dyes, and other dyes and pigments. Examples of these include carbon black, titanium oxide, iron oxide,
Powders of various metals and compounds such as metal oxides and sulfides, pigment black (C, L50440), chrome yety-lite (C, 1,77603), 2,2'-dihydroxy-4-methoxybenzophenomer, 2.4-Dihydroxybenzophenonehydrovxyphenylbenzotriazole, 2-(2'-Hydenoxy5'-methoxyphenyl)benzotriazole, resorcinol monobenzoate, ethyl-2-cyano-3,3-diphenyl acrylate, Toluidine Yellow-GW (C, 1,
71680), molybdenum orange (C, 1,7760)
5), Sudan Yellow (C, 1, 30), and #Iru Orange (C, 1, 12055). In particular, carbon black is desirable in order to achieve the same black color as conventional silver salts. Furthermore, if a non-colored ultraviolet absorber is used, it is better to add dyes or pigments since the image area will be difficult to see.

In the case of inorganic/organic pigments, metals, and metal compounds, it is necessary to make them into fine particles by physical or chemical methods.

Note that the actinic ray absorber is not contained in the photosensitive resin layer and an intermediate layer is provided in the undercoat layer or between it and the photosensitive layer,
It may also be incorporated therein to form a colored image reproduction material.

In the present invention, the thickness of the photosensitive resin layer is not limited to the photosensitive resin layer that provides an image formed product consisting of a cured upper layer portion and an uncured lower layer portion as described in detail above, but is also suitable for precise image reproduction. When used for various purposes, the thickness is preferably 1 to 6μ, but in the case of image duplication materials for special uses, such as photosensitive resin letterpress or photosensitive resin letterpress materials for making paper molds and matrix molds, the thickness Of course, even if the thickness reaches several hundred microns, it will still work effectively.

Next, the scratch-resistant layer in the present invention will be explained in detail.

Compounds that form a scratch-resistant layer alone or in combination with other compounds (hereinafter referred to as scratch-resistant improvers)
is one or more selected from silane coupling agents, silicone oils, and silicone greases.

The silane coupling agent has the general formula Y + O+1+ Ri +nIS i + OR2)
n, specifically (CHa)a-n vinyldria heptoxysilane, vinyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, r-aminopropyltriethoxysilane, N- β-(aminoethyl)-γ-aminopropyltriethoxysilane, r-methacryloxypropyltrimethoxysilane, r-glycidoxyp4pyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltris-(β-methoxyethoxy)silane ,
N-β-(aminoethyl)-γ-aminopropyl-methyldimethoxysilane, γ-chlorobutibyltrimethoxysilane, r-mercaptopropyltrimethoxysilane,
Examples include methylhydrogensiloxane.

Silicone oils include linear dimethylpolysiloxane, di-n-propylpolysiloxane, diphenylborisiloxane, and methylaenylborisiloxane with a relatively low degree of polymerization. There are xane, etc., and it is a mixture of substances with various molecular weights.

The silicone grease is a mixture of the silicone oil and a metal soap such as sodium stearate or lithium stearate, or a mixture of fatty acid diester.

In addition to the above-mentioned compounds, aliphatic compounds may also be used in the scratch-resistant layer.

In the present invention, the layer containing the scratch resistance improver can exhibit the greatest effect if it is a molar layer or a multi-layer of the improver, but for practically sufficient scratch resistance, it is not necessary to use a molar layer. There is no need for a layer of scratch resistance improver to be as dense as this. The amount of the scratch resistance improver forming the scratch resistance layer can be determined by surface spectroscopic analysis methods such as photoelectron spectroscopy and Raman scattering, or by selectively scraping off the layer and by liquid fluoratography or gas chromatography. Quantitative analysis is possible by performing a quantitative analysis, but as a result of the research conducted by the present inventors using such analytical means, the amount of the improver in the scratch-resistant layer that is preferable for improving scratch resistance is It ranges from 0.08 to 509 per In” on the surface. 50
Even if it exceeds ff9, it is very effective for improving scratch resistance, but the reproduction accuracy (resolution, etc.) of the image reproduction material
On the other hand, if O,OS is not reached, the degree of improvement in scratch resistance that can be expected is not satisfactory from a practical point of view.

In the present invention, the layer consisting of the scratch resistance improving agent as described above can be formed by coating a solution of the scratch resistance improving agent on the photosensitive resin layer and drying it, or directly exposing it to light using a vacuum evaporation method. This method can be obtained by forming a scratch resistance improver on a photosensitive resin layer, or by coating a photosensitive resin layer with a protective layer containing the scratch resistance improver. A scratch resistance improver is added to the photosensitive resin composition at the time of molding (film) by hot melt extrusion onto a support with or without undercoating, or by solution coating and drying. It is preferable that the scratch resistance improving agent in the photosensitive resin layer is migrated to the surface of the photosensitive resin layer to form a scratch resistant layer. When such a formation method is used, the amount of the scratch resistance improver in the entire photosensitive resin composition is preferably 0.35 to 10% by weight based on the composition, preferably 0.4 to 10% by weight.
It is necessary that the content be 5% by weight. If the blending amount is less than 0.35% by weight, the amount migrating to the surface of the photosensitive resin layer will be extremely small, and no substantial effect of improving scratch resistance can be expected. When the amount exceeds 10% by weight, it is clear that the scratch resistance is effective, but the layer of the scratch resistance improver becomes too thick and scatters or blocks light, making it difficult to use as an image duplicating material. This is undesirable from the viewpoint of replication accuracy.

In this way, when forming a scratch-resistant layer on the surface of a photosensitive resin layer by blending the scratch resistance improving agent into a photosensitive resin composition and molding (forming a film), the photosensitive resin composition When the scratch resistance improving agent is in a dry state, that is, containing 100 ppm or less of coating solvent, water, etc., the migration rate of the scratch resistance improver is maintained at room temperature or at 60%.
It needs to be soft enough to tolerate r+ at temperatures below 'C. The softness of the photosensitive resin layer can be determined by molding the photosensitive resin composition into a film of 20 to 30 μm and subjecting it to thermomechanical analysis in a dry state.
lysis: TMA), plot the elongation of the film against temperature, and define the flow start temperature as the intersection of the tangent of the part where the elongation passes the inflection point and grows to a straight line and the temperature axis. It can be measured by

(Kobunshi Papers, Vol. 38 P. 479 (1981)
)) In the present invention, when the scratch resistance improver is blended into the photosensitive resin layer and the scratch resistance layer is formed by migration after molding (or film formation), the flow start temperature of the photosensitive resin composition The preferred limit is 95°C or lower. This is because if the temperature is higher than 95° C., the migration rate becomes extremely slow, making it impractical.

In the present invention, the photosensitive resin layer has good light transmittance and is removable for the purpose of preserving the surface or preventing inhibition of the photopolymerization reaction by oxygen, especially when the photosensitive resin layer is a photopolymerization type. It may be coated with a protective film or a protective layer soluble in an aqueous solvent. Therefore, resins such as polyvinyl alcohol, polyacrylic acid, and methyl cellulose that are soluble in aqueous solvents can be used. In particular, polyvinyl alcohol is preferred because it has excellent oxygen barrier properties and can reduce the radical polymerization damage prevention effect caused by oxygen.

In producing the image duplicating material of the present invention, a photosensitive resin layer is formed by melt molding or a film forming method, or by a solution coating method, on a support that has a subbing layer in advance, if necessary, and then dried. Scratch resistance can be improved by applying a scratch resistance improver to the surface of the obtained photosensitive resin layer by vacuum deposition or coating, and then laminating a protective film or coating a protective layer as necessary, or as described above. A photosensitive resin layer containing an improving agent is formed on the above support by melt molding or a film forming method, or by a solution coating method and is dried to form a photosensitive resin layer, and then a protective film is applied as necessary. Obtained by laminating or by coach-inking a protective layer. In the latter manufacturing method, when providing a protective layer, there is no limit to the time between forming the photosensitive resin layer and coating the protective layer, but if coating is performed after several hours, the protective layer may be coated. It is preferable to contain a surfactant or the like. The image forming material of the present invention thus produced is used in the following manner.

If the photosensitive resin is of a photocurable type, that is, one that utilizes photodecomposition insolubilization reaction, photocrosslinking reaction, or photopolymerization reaction, it should be placed in close contact with the transparent original, and an ultra-high-pressure mercury lamp, metal halide lamp, etc. with a rich amount of actinic rays may be used. Expose to light. Thereafter, it is developed using a developer. If a protective film is present, it is peeled off, and if a protective layer is present, uncured portions of the protective layer and the photosensitive resin layer that are not exposed to light are eluted.

When the subbing layer uses a thin film of metal or metal compound, the exposed metal or metal compound layer is eluted by developing the photosensitive resin layer with an etching solution to create an image whose black and white are reversed from the printed original. obtain.

It is also possible to finish the final image by processing the entire layer in one solution by using both the developer for the photosensitive resin layer and the etching solution for the layer below it. ◇ Use a photodegradable and solubilized type of photosensitive resin. In this case, a developer for the photosensitive resin layer is used to elute the portion of the photosensitive resin layer that has been irradiated with actinic rays and photodecomposed, and if there is a protective layer, the protective layer is eluted.

When the subbing layer utilizes a thin film of a metal or metal compound, the exposed metal or metallized metal layer is then eluted by developing the photosensitive resin layer with an etching solution;
Obtain the same image as the printed original. In this case, it is also possible to use both the developer and the etching solution and finish with the -solution.

The rotational reproduction material of the present invention can be printed! II! Plate film (
It can be used for various purposes such as so-called lithography film for turning back), photomasks, photosensitive films for color proofing, PS plates for planographic printing, and photosensitive resin letterpress materials.

Especially active light! A photopolymerizable system comprising a l1ffi astringent,
In the case of the image duplicating material of the present invention having a photosensitive resin layer which provides an H-image forming product consisting of a cured upper layer part and an uncured lower layer part after image exposure and development, if necessary, post-development reduction force (dot etch) is applied. It can be performed. The reduction process is performed by spraying with the same solvent as the developer or a diluted solvent, or by rubbing with a sponge or brush in the solvent, but usually a fixing process is performed after development and before the reduction process. It is preferable. Such a reducible image duplicating material is particularly suitable as a printing plate-making film or a photosensitive film for color proofing.

Since the present invention has the above-mentioned configuration, it has the following features: (1) The scratch resistance of the image surface after image formation has been significantly improved, so there is no possibility of scratches occurring during handling operations. decreased to

(2) There is no need to worry about deterioration of image duplication performance such as degree of resolution, resolution, and developability.

(3) There is no adverse effect on storage stability (shelf life), which is an important performance item as an image duplication material.

(4) Even in image duplicating materials that can be reduced in force, the force reduction performance (
There is almost no effect on the power reduction rate or speed.

(5) Does not adversely affect adhesive tape, opaque, staging varnish, etc. used in post-processing.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 A polyester film having a thickness of 100 μm was coated with the following composition using a reverse coater and dried to produce a polyester film having a 0.5# lower σ1 layer.

Cornate L (manufactured by Nippon Polyurethane Industries) 4 parts U-C
at SA-m102 (manufactured by San Abbott) 0.1 parts Toluene 80 parts Methyl ethyl ketone 20 parts Next, a photosensitive composition was prepared by mixing and dispersing the following composition, and a polyester coated with the above-mentioned undercoat layer was prepared using a reverse coater. Coating each on the film, thickness 3
Methyl methacrylic acid copolymer coated with μ photosensitive layer 41 parts Carbon black 12 parts Trimethylpvapane triacrylate mixture Diphenylimidazolyl dimer Scratch resistance improver shown in Table 1 Amount shown in Table 1 Hydrodecenone monomethyl ether O, Oa part dimedone 3
Part Michler's ketone 2.0 parts Methanol 140 parts Chloroform 120 parts Ethyl acetate 80 parts n-propyl acetate 40 parts Isopropyl alcohol 40 parts Furthermore, a composition for a protective layer having the following composition was coated on this film in the same manner. An image reproduction material was prepared with a protective layer of 1μ in thickness.

Polyvinyl alcohol 5 parts (degree of saponification 98.5%, degree of polymerization 500) Neugen EA-
140 (No. 1 - Industrial Pharmaceutical Department) 0.2 parts Methanol 5 parts Water 90 parts A test negative film with a halftone image was placed on top of the film, and the image was exposed for a predetermined period of time using a bright room printer (manufactured by ORC).

Next, after removing the protective layer by washing with water, immerse the sample in (A) 0.75% NagCOa aqueous solution adjusted to 30°C for 10 seconds, wash with water, develop while rubbing with a sponge, and dry to obtain a reversed image. I got it. It was found that up to the 5th step of the step guide was cured, and the halftone dots reproduced the negative well.

Next, a duplicate halftone image made in the same manner was immersed in a 5% aqueous solution of hydroquinone kept at 30°C for 15 seconds, and then washed with water.
Dry treated.

The thus obtained sample was subjected to a scratch test under load using a surface property tester type He1don-14 manufactured by Shinto Kagaku-1 with a sapphire needle of 0.1XΩ at a speed of IUOX/min. It is also listed in Table 1.

As is clear from Table 1, it was found that the scratch resistance of the image surface was greatly improved by using the method of the present invention.

Kei l Example 2: After cleaning and drying the surface of a 100μ thick polyester film, it was heated to 1G'T using a resistance heating vacuum evaporator.
Aluminum was deposited to a thickness of 500x under vacuum on an orr table.

Next, a photosensitive composition shown in Table 2 was prepared and coated on the aluminum-deposited polyester film using a reverse coater to form a 3 μm thick photosensitive layer.

Furthermore, this film was similarly coated with a composition for a protective layer having the composition shown below to prepare an image duplicating material having a protective layer having a thickness of 1 μm.

Polyvinyl alcohol 5 parts (degree of saponification 98.5%, degree of polymerization 500) Neugen EA-
14a (No. Industrial Pharmaceutical Department) 0.2 parts methanol 5 parts water. A 21-step step guide (manufactured by Dainippon Screen Co., Ltd.) and a test negative film of 150 t/in and 50% halftone dots were layered on the obtained image duplication material, and a bright room printer (manufactured by ORC Co., Ltd.) was used. Image exposure was performed for a predetermined time. Next, after removing the protective layer by washing with water, the Nln
(A) 10% in 0.75% Na2COa aqueous solution
After dipping for a second, washing with water and developing while rubbing with a sponge,
The unexposed areas of the photosensitive resin layer were removed, and then immersed in a second developing solution of a saturated calcium hydroxide solution (30°C) for 3 minutes, washed with water, and then immersed in a 5% aqueous solution of hydroquinone (30°C).
0° C.) Ir=1 s, washed with water, and dried to obtain a sample for scratch resistance measurement.

When the obtained sample was subjected to a scratch test under load in the same manner as in Example 1, the strength shown in Table 2 was obtained.

Table 2 As is clear from Table 2, it was found that by using the method of the present invention, the scratch resistance of the image surface was greatly improved.

Example 3゜On the polyester film having the subbing layer of Example 1,
Each of the scratch resistance improvers shown in Example 3 was added to the composition solution in Example 1 except for the scratch resistance improver, and the resultant mixture was coated with a reverse coater and dried to form a photosensitive layer with a thickness of 3μ. coated. Furthermore, a protective layer having a thickness of 1 μm was formed on each film in the same manner as in Example 1.

Materials for evaluating scratch resistance were prepared in the same manner as in Example 1, and the scratch strength was measured as in Example 1, and the results shown in Table 3 were obtained.

Table 3 Example 4 A polyester film having a thickness of 100 μm was coated with the following composition using a reverse footer and dried to produce a polyester film having a subbing layer of 0.5 μm.

Byron 20S saturated polyester adhesive 50 parts (manufactured by Toyobo → Coronate L (manufactured by Nippon Polyurethane Industries) 4 parts U-C
at SA N1102 (manufactured by San Abbott) 0.1
Part toluene 80 parts Methyl ethyl ketone 20 parts Next, a colored resin was prepared by mixing and dispersing the following composition, and it was coated on the polyester film provided with the undercoat layer using a reverse footer to form a colored resin layer with a thickness of 2μ. Ta.

Copolymer of methyl methacrylate and methacrylic acid 41 parts Carbon black 12 parts Methanol 140 parts Ethyl acetate 80 parts n-propyl acetate 40 parts Isoprevyl alcohol 40 parts Furthermore, on this film, a photosensitive composition having the following composition was applied. was prepared and coated using a reverse coater to form a photosensitive layer with a thickness of 1 μm.

Copolymer of methyl methacrylate and methacrylic acid 41 parts 2-(2-chloro-1-naphthyl)4.5-diphenylimitasol) 2fmsm Silane coupling agent listed in Table 4 Hydroginone monomethyl ether 0.03 parts Dimedone 3 parts Michler's ketone 2 parts Methanol 140 parts Chloroform 120 parts Ethyl acetate 80 parts n-propyl acetate 40 parts Isopropyl alcohol 40 parts Furthermore, a protective layer composition having the following composition was similarly coated on this film to a thickness of 1 μm. An image reproduction material was prepared having a protective layer of .

Polyvinyl alcohol 5 parts (Saponification degree 98.5% Polymerization degree 5oo) Neugen rA-z4o (Daiichi Kogyo Seiyaku) 0.2 parts Methanol 5 parts Water 90 parts The same treatment as in Example 1 was carried out to evaluate scratch resistance. Data were prepared and a one-stroke test was conducted as in Example 1, and the results shown in Table 4 were obtained. It can be seen that all of these scratch resistance improvers are effective.

Table 4

Claims (1)

[Scope of Claims] +il An image duplicating material having at least a photosensitive resin layer, a scratch-resistant layer and a protective layer on a support, the scratch-resistant layer having the general formula Y + O+t+Rt
- Silane force (CHa)s represented by Hori81÷0R2)□
-n An image duplicating material characterized by containing one or more selected from a tumbling agent, silicone oil, and silicone grease. (And indicates a halogen atom.) +21 7F! ! The image reproduction material according to claim 1, wherein the photoresin layer contains a photoinitiator, a monomer, a binder and an actinic ray absorber. (3) In a method for producing an image duplicating material by laminating or coating at least a photosensitive resin layer and a protective layer on a support, the photosensitive resin layer has the general formula Y + O+z (
-Rx +m81 (-ORz). Silane power (CH3) 11-n represented by Method of manufacturing materials.