JPH0327107B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to image reproduction materials capable of providing images with improved productivity and 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 redoing the entire process. There is a problem that a huge amount of time and materials are lost. This 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 duplicating materials that utilize photosensitive resins are very advantageous in terms of brightness resolution, safety, and cost, and resolving the lack of scratch resistance has been a long-standing issue. At present, the situation has been overcome by techniques such as after-baking after image formation and resin coating, but nothing has been found that essentially solves this problem by going back to the structure of the image duplicating material. The present inventors have conducted research on the microstructure of image duplicating materials that significantly improves the scratch resistance of images formed under such circumstances, and have developed images in which a thin layer of a scratch resistance improving agent is provided on a photosensitive resin layer. He invented a reproduction material and has already applied for a patent. Although the effects of the invention were overwhelming, there is one serious obstacle in producing such materials in large quantities efficiently and with stable performance and commercializing them into commercial products.
This can be seen when coating a protective layer on an image recording layer provided with such a scratch-resistant layer, and the coating may not be achieved uniformly, or even if it is coated uniformly, it cannot be exposed to light as an image duplicating material.
The improvement in scratch resistance that would be expected when performing image duplication such as development may not be observed, or the adhesiveness between the protective layer and the scratch resistance may be insufficient and it may peel off easily during handling. be.
Since such a phenomenon poses a serious problem for the commercialization of this material, the present inventors have made further efforts to improve these points, and as a result, have finally completed the present invention. That is, the present invention provides an image duplicating material having at least a photosensitive resin layer and a protective layer on a support, in which the protective layer is a thin film of a polymeric substance, and the cationic resin layer has a weight ratio of 1:10 to 5:1. The image duplicating material is characterized in that the polymer substance contains 0.5 to 10% by weight of a surfactant and a nonionic surfactant. Supports suitable for use in the image reproduction material in the present invention include glass plates, plastic films, metal plates, papers and the like. Examples of the plastic film include films of polyester, polypropylene, polyethylene, polyvinyl chloride, polyvinylidene chloride, polycarbonate, cellulose acetate, and the like. In particular, a biaxially stretched polyester film is preferred because it has excellent dimensional stability and transparency. Although there is no strict limit to the thickness of the support, a thickness of 75 to 175μ is suitable. In the present invention, the effect is observed even when the support is in direct contact with the photosensitive resin layer, especially when the support is impregnated with an adhesive compound that can improve the adhesive strength to the photosensitive resin layer. However, a generally preferred structure is one having 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 thin layers include, for example, polyacrylate, polyvinylidene chloride/acrylonitrile/itaconic acid copolymer, vinyl chloride/vinyl acetate/maleic anhydride copolymer, terephthalic acid/isophthalic acid/glycol copolymer, and Examples include thin films of polymeric substances such as isocyanate compounds. The layer thickness is usually 0.2-2μ. 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, rhodium, selenium, silver, tantalum, tin, tungsten, vanadium, zinc, zirconium, etc., and alloys, oxides, nitrides, borides, carbides, sulfides, and salts of the above metals. Examples include aluminum, 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,
There are methods such as ionization electrostatic plating. The thickness of the metal or metal compound varies depending on the type of metal or metal compound, and is usually 100 to 1000 Å, preferably 300 to 600 Å. The photosensitive resin mentioned in the present invention refers to a resin that rapidly undergoes a physicochemical change upon irradiation with actinic rays to change its solubility in a developer, or that produces a visible image as it is or after processing. However, from the point of view that the reason for providing a protective layer is generally to prevent the inhibition of photoreactions by oxygen, the most important effect is exhibited in photopolymerization systems where oxygen has a large inhibition effect. The photopolymerizable photosensitive resin referred to herein is one whose main component is a polymeric binder, a monomer or oligomer having an ethylenically unsaturated bond, and a photoinitiator. Such a photopolymerizable photosensitive resin may be visually transparent, and even if it contains a coloring agent such as a dye pigment or a light shielding agent, the effects of the present invention can be similarly achieved. It is. The present invention exhibits a particularly effective effect because it provides 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. In this method, a photosensitive resin containing a substance that can act as an actinic ray absorber is used. Since the image formed by such a photosensitive resin layer has an uncured lower layer, the lower layer is likely to be destroyed by scratches on the surface, and unless the structure of the present invention is used, the surface will not be practical. This is because it is impossible to achieve the same scratch resistance. The above-mentioned coloring agent or actinic ray absorber includes an ultraviolet absorber, an ultraviolet absorbing dye, and other dyes and pigments. Examples of these include powders of compounds such as carbon black, titanium oxide, iron oxide, various metals and metal oxides, and sulfides, pigment black (C.1.50440), chrome yellow light (C.1.77603), 2,2 '-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone hydroxyphenylbenzotriazole, 2,(2'-hydroxy-5,-methoxyphenyl)benzotriazole, resorcinol monobenzoate, ethyl-2 -Cyano-3,3'-diphenyl acrylate, toluidine yellow GW
(C.1.71680), Molybdenum Orange (C.1.77605),
These include Sudan Yellow (C.1.30) and Oil Orange (C.1.12055). In particular, carbon black is desirable in order to achieve the same black color as conventional silver salts. For the purpose of simply coloring an image, there is a method in which the above-mentioned coloring agent or actinic ray absorber is mixed with a polymeric binder as an intermediate layer, and a transparent photosensitive resin layer is formed thereon. is also valid. Examples of polymeric binders used for this purpose include those shown below, which are also effective as polymeric binders for photosensitive resins. Cellulose esters and ethers, 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 Examples include polyvinyl esters and copolymers thereof, phenolic resins, polyvinylidene compounds, polyvinyl alcohols, gelatin and derivatives thereof, polyvinyl petyral, polyacrylamide, polyvinylpyrrolidone, polystyrene, chlorinated rubber, polyethyleneimine, and the like. Particularly, in order to enable development with an aqueous developer, the binder itself must 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 methyl ether succinate, methacrylic acid, acrylic acid, maleic acid, maleic anhydride, and itacon. acid,
Examples include copolymers of crotonic acid and vinyl monomers, copolymers containing sulfonic acid groups, polyesters containing tertiary nitrogen groups, polyamides, and polyether polyvinyl polymers. In addition, when the above-mentioned binder is used as a binder for a photosensitive resin layer, it may contain a polymerizable unsaturated double bond group in its main chain or side chain. 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 detailed above, but is also suitable for precise image duplication purposes. If used, 1~
10μ is preferred, but in the case of image duplicating materials for special uses, such as photosensitive resin letterpress or photosensitive resin letterpress materials for making paper molds and matrix molds, the thickness may reach several hundred μ. Of course, this also works effectively. In addition, when a colorant or the like is blended into the intermediate layer and a transparent photosensitive resin layer is provided thereon, the intermediate layer is
15μ, and the photosensitive layer preferably has a thickness of 0.5 to 10μ. Next, the protective layer used in the present invention will be explained. The protective layer is provided for the purpose of protecting the surface of the image duplicating material or blocking oxygen, especially when the photosensitive resin layer is one that is subject to inhibition of photoreaction by oxygen, such as a photopolymerizable resin layer. Such a protective layer is formed on the photosensitive layer by coating mainly with a polymeric substance, but it is preferable that it has good light transmittance to actinic rays and can be removed at the same time as the photosensitive resin layer is treated. Examples of such polymeric substances include amides of higher fatty acids;
These include waxes, rubbers, polystyrene, chlorinated polyolefins, etc. Particularly preferred are those soluble in aqueous solvents, for example,
Resins such as polyvinyl alcohol, polyacrylic acid, methylcellulose, etc. can be used. Polyvinyl alcohol is particularly preferred because it has excellent oxygen barrier properties and can reduce the radical polymerization damage prevention effect caused by oxygen. In the present invention, a cationic surfactant and a nonionic surfactant are used as protective layer components in a total amount of 0.5 to 10% by weight based on the polymeric substance.
It is necessary to blend it, preferably 1 to 7% by weight. It cannot be said that either one alone, or an anionic surfactant or an amphoteric surfactant, alone or in combination with a nonionic surfactant, is completely ineffective, but it is difficult to eliminate all of the above-mentioned problems. It cannot be done. Examples of cationic surfactants include alkylamine halogenates, quaternary ammonium salts, alkylpyridinium halides, alkylbedines,
Amine oxide etc. can be used, and more specifically, coconut amine acetate, stearyl amine acetate, stearyl amine hydrochloride, stearyl amine oleate, lauryl amine oleate, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, alkyl It mainly consists of benzyldimethylammonium chlorite, lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, etc. Examples of nonionic surfactants include polyethylene glycol-based and polyhydric alcohol-based surfactants, and more specific examples include polyethylene glycol nonyl phenyl ether, polyethylene glycol octyl phenyl ether, polyethylene glycol decyl phenyl ether, and polyethylene glycol. Glycol oleyl ether, polyethylene glycol lauryl ether, polyethylene glycol stearyl ether, polyethylene glycol higher alcohol ether, polypropylene glycol polyethylene glycol ether, sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, sorbitan monooleate, polyethylene glycol alkyl quine Examples include ether. It is preferable that the mixing ratio of the cationic surfactant and nonionic surfactant is in the range of 1:10 to 5:1. When the blending ratio (weight ratio) of the cationic surfactant is less than 1:10, the adhesion with the photosensitive layer is insufficient, and when it is more than 5:1, the scratch resistance of the surface after image formation is expected to be poor. This is not preferable because the improvement will not improve as much as possible. Furthermore, if the total amount is less than 0.5% by weight, uniform coating becomes difficult;
When the amount is more than 1, a sufficient effect can be expected, but it is not preferable because it destroys the balance with other performances in terms of oxygen permeability, transparency, etc. of the protective layer. Even if the protective layer in the present invention contains a third component such as silica powder or polyethylene emulsion in addition to the above-mentioned polymeric substance and combined surfactant, the same effect of the present invention can be expected. can. The image duplicating material of the present invention having the above-mentioned structural requirements has improved coating properties, adhesive properties, etc. of the protective layer, and has good productivity.However, in order to further improve scratch resistance, it is necessary to Preferably, a scratch-resistant layer is provided between the resin layer and the protective layer. The scratch resistance is formed by a compound represented by the structural formula Am-Bn (hereinafter referred to as a scratch resistance improver), where A is a monovalent or divalent optionally branched carbon number of 12 to 20. B is an aliphatic hydrocarbon group, B is a hydroxyl group, an amino group, a nitrile group, an aldehyde group, a carboxy group, an alkyl amide, an alkyl ester, or an ammonium of a carboxylic acid, or a salt of a metal of Groups ~ of the periodic table, and m is 1, 2 or 3; n represents 1 or 2; Examples of such scratch resistance improvers include aliphatic hydrocarbon monocarboxylic or dicarboxylic acids, specifically lauric acid,
n-tridecylenic acid, myristic acid, n-bentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, linoleic acid, elaidic acid, n-nonadecylenic acid, arachidic acid, paraxic acid, eicosenoic acid, trans-2-dodecene acids, isostearic acid, 2-nonaheptylundecanoic acid, 1-16 hexadecanedioic acid, 1,20 eicosandioic acid, etc. The derivatives of the aliphatic hydrocarbon carboxylic acids are listed in the periodic table. There are salts or alkyl esters with metals of group ~, and the alkyl esters include esters of these carboxylic acids with methyl, ethyl alcohol, etc., and esters with polyhydric alcohols such as glycol and glycerin, such as glycol laurate and lauric acid. Glycerin ester, glycerin myristate, glycerin myristate, glycerin palmitate, glycerin palmitate ester, glycol stearate, glycol distearate, glycerin stearate, and the like are effective. Vinyl stearate is also effective as the vinyl ester. Alkylamides are effective as carboxylic acid derivatives other than those listed above, such as lauramide, tridecylamide, palmitic acid amide,
These are 2-heptadecenic acid amide, stearic acid amide, and arachidic acid amide. Other examples of scratch resistance improvers are aliphatic hydrocarbon alcohols, aldehydes, amines and nitriles. For example, alcohols include lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, and arachine alcohol. Examples of aldehydes include lauric aldehyde, dodecyl aldehyde, myristic aldehyde, pentadecyl aldehyde, tridecyl aldehyde, heptadecyl aldehyde, and stearic aldehyde. As amines, laurylamine, myristylamine,
pentadecylamine, stearylamine, etc. Examples of the nitrile include laurylonitrile, tridecylnitrile, myristonitrile, palmitonitrile, and stearonitrile. These materials may be used alone, but they are also effective when used in combination. In the present invention, preferable scratch resistance improvers include a monovalent hydrocarbon group having 11 to 20 carbon atoms as A, and a carboxyl group as B, specifically stearic acid, lauric acid, tridecylic acid, myristic acid. , pentadecanoic acid, palmitic acid, heptadecanoic acid, nonadecanoic acid, arachidic acid, n-
and their alkyl esters. In the present invention, the layer consisting of the scratch resistance improver can exhibit the greatest effect if it is a monolayer or multilayer of the improver, but for practically sufficient scratch resistance, it is not necessary to use a monolayer layer. It does not need to be a dense layer of scratch resistance improver, such as . The amount of the scratch resistance improving agent 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 chromatography or gas chromatography. Quantitative analysis is possible by performing photography, and as a result of 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 the scratch resistance is determined by the photosensitive The amount is in the range of 3×10 ⁻⁷ mol to 1.75×10 ⁻³ mol per m ³ of the surface of the resin layer. If it exceeds 1.75×10 ^-3 mol/m ³ , it is very effective in improving scratch resistance, but it is not preferable from the viewpoint of reproduction accuracy (resolution, etc.) of the image duplicating material. If the amount does not reach ^-7 mol/m ³ , 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 improver as described above can be formed by coating a solution of the scratch resistance improver on the photosensitive resin layer and drying it, or directly exposing it to light using a vacuum evaporation method. The scratch resistance improver can be formed on the photosensitive resin layer, or by coating the photosensitive resin layer with a protective layer containing the scratch resistance improver, but the most effective method is to form the scratch resistance improver on the photosensitive resin layer. A scratch resistance improver is added to the photosensitive resin composition at the time of molding (film) by hot melt extrusion or solution coating and drying onto a support with or without a subbing layer. 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 scratch resistance. When such a formation method is used, the amount of the scratch resistance improver in the entire photosensitive resin composition is 0.35 to 10% by weight, preferably 0.4 to 5% by weight based on the composition. It is necessary. 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 it is effective for scratch resistance, 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 the scratch resistance improving agent is blended into a photosensitive resin composition, molded (film formed), and then migrated to form scratch resistance on the surface of the photosensitive resin layer, the photosensitive resin composition is mixed with the scratch resistance improving agent. Ensure that the resin layer is dry, i.e. free from coating solvents, moisture, etc.
It is preferable that the scratch resistance improver has a softness that allows migration of the scratch resistance improver at room temperature or at a temperature of 60° C. or lower when the scratch resistance improver is contained at 100 ppm or less. The softness of such a photosensitive resin layer can be obtained by molding a photosensitive resin composition into a film of 20 to 30μ.
Therme mechanical analysis in dry state
Analsis (TMA) is carried out, and the elongation of the film is plotted against the temperature, and the point where the tangent line of the part where the elongation passes the inflection point and grows significantly and becomes a straight line and the temperature axis intersects is defined as the flow start temperature. It can be measured by (Polymer Papers, Vol.38p.479
(1981)) In the present invention, when the scratch resistance improving agent is blended into the photosensitive resin layer and the scratch resistance layer is formed by migration after molding (or film formation),
A preferred limit for the flow initiation temperature of the photosensitive resin composition is 95°C or lower. This is because if the temperature is higher than 95°C, the migration rate will be extremely slow, making it impractical. 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. A scratch resistance improver is applied to the surface of the photosensitive resin layer obtained by drying by vacuum deposition or coating, and then, if necessary, a protective film is laminated or coated with a protective layer, or as described above. A photosensitive resin layer containing a scratch resistance improver 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 layer is coated. It can be obtained by In any of the manufacturing methods, when a protective layer is provided by coating, if a layer of a scratch resistance improver is already present on the surface of the photosensitive layer, this becomes an important factor in terms of coating behavior and final product performance. The problems that occur are not only that the protective layer solution is repelled and does not adhere uniformly, but also that in some cases, even if a uniform coating is achieved, the expected effect of the scratch resistance improver may not be obtained. Alternatively, the protective layer may peel off due to small shocks during handling of the reproduction material, although it exhibits uniform coating properties. These failures are probably the result of a complex interaction between the protective layer solution, the scratch-resistant layer, and the photosensitive resin layer, rather than being due to a single cause. The present invention provides a definitive solution to these obstacles. The image duplicating material of the present invention having the above-mentioned configuration can be used to faithfully reproduce an image using a conventional method, and can be used as a film for printing plates, a photomask, a photosensitive film for color proofing, a PS plate for planographic printing, a photosensitive resin letterpress material, etc. It can be used for various purposes and has the following features. (1) The scratch resistance of the image surface after image formation has been significantly improved, and the risk of scratches occurring during handling has been extremely reduced. (2) There is no need to worry about deterioration in image duplication performance such as sensitivity, developability, resolution, etc. (3) There is no adverse effect on storage stability (shelf life), which is an important performance item for image duplication materials. (4) Even in image duplicating materials that can be reduced in force, there is almost no effect on the reduction performance (force reduction %, speed). (5) It is an image duplicating material that has a protective layer that exhibits excellent gloss and excellent adhesion to the photosensitive layer, and that provides images that consistently exhibit stable scratch resistance. (6) In particular, when used as a photolithographic film, conventional materials and methods can be used for adhesion to cellophane tape, opaque coating properties, applicability to staging varnish, etc., which are often used in the photolithography process. Hereinafter, the present invention will be specifically explained using examples. Note that "middle part of the example" refers to parts by weight unless otherwise specified. Example 1 A polyester film having a thickness of 100μ was coated with the following composition using a reverse coater and dried to produce a polyester film having a subbing layer of 0.5μ. Byron 20S saturated polyester adhesive 50 parts (manufactured by Toyobo Co., Ltd.) Coronate L (manufactured by Nippon Polyurethane Industries) 4 parts U-cat SA-No.102 (manufactured by Sunabott Co., Ltd.) 0.1 part Toluene 80 parts Methyl ethyl ketone 20 parts Next, the following composition was prepared. A photosensitive composition was prepared by mixing and dispersing the above, and was coated on the polyester film provided with the undercoat layer using a reverse coater to form a photosensitive layer having a thickness of 3 μm. Copolymer of 73.5 mol% methyl methacrylate and 26.5 mol% methacrylic acid 41 parts carbon black 12 parts tetraethylene glycol dimethacrylate
17 parts Trimethylolpropane triacrylate 17 parts 2-(2-chloro-1-naphthyl)4,5-diphenylimidazole dimer 8 parts Scratch resistance improver listed in Table 1 3 parts Hydroquinone monomethyl ether 0.03 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 Further, a protective layer composition having the following composition was coated on this film in the same manner.
An image reproduction material with a 1μ protective layer was prepared. Polyvinyl alcohol 5 parts (degree of saponification 98.5%, degree of polymerization 500) Surfactant mixture listed in Table 1 Quantity listed in Table 1 Methanol 5 parts Water 90 parts Obtained image duplication material samples No. 1 to 4, No. 7 ~9,
No. 12 to 14 each have a 21-step step guide (manufactured by Dainippon Screen Co., Ltd.) with a dot area ratio of 150/in and a dot area ratio of 50.
% of the test negative film combined, and using a bright room printer (manufactured by ORC),
Image exposure was performed for a predetermined time. Next, after removing the protective layer by washing with water, the temperature was adjusted to 30℃ (A) 0.6%
After immersing it in a Na ₂ CO ₃ aqueous solution for 10 seconds, washing with water and developing and drying while rubbing with a sponge, a reversed image was obtained. It was found that up to the 5th stage 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 for 15 seconds in a 5% aqueous solution of hydroquinone kept at 30°C, washed with water, and dried. The sample thus obtained was subjected to a scratch test under load at a speed of 100 m/m/min with a sapphire needle of 0.1 m/mφ using a surface property tester type Heidon-14 manufactured by Shinto Kagaku Co., Ltd. The obtained results are shown in Table 2 together with other evaluation items. Other evaluation items were based on the following criteria. Coating properties of the protective layer: Can be coated completely uniformly. 〇Although it can be applied evenly, some small depressions may appear on the surface. △Cannot be coated uniformly, resulting in splashed areas without a protective layer. ×It is impossible to apply a protective layer due to complete repellency. Adhesion between the protective layer and the photosensitive layer: When cellophane tape is applied to a protective layer and peeled off vertically by holding one end, the protective layer to be peeled off is almost limited to the area where the cellophane tape is applied, and peeling is difficult. △It can be easily peeled off using the above method, and the peeled area will be at least 10 cm from the edge of the cellophane tape. ×Even without cellophane tape, the protective layer can be completely peeled off simply by holding both ends of the film and shaking it. Comparative Example 1 Image duplication material samples Nos. 5, 6, 10, and 11 were obtained in exactly the same manner as in Example 1, except that the surfactant in the protective layer composition was changed to one listed in Table 1. Ta. The obtained samples were evaluated in exactly the same manner as in Example 1, and the results are also listed in Table 2.

【table】

【table】

[Table] As is clear from Table 2, the image duplicating material samples of the present invention Nos. 1 to 4, 7 to 9, and 12 to 14 have good coating properties of the protective layer, adhesion between the protective layer and the photosensitive layer, and scratch resistance. It can be seen that both sexes are excellent.

Claims (1)

[Scope of Claims] 1. An image duplicating material having at least a photosensitive resin layer and a protective layer on a support, wherein the protective layer is a thin film of a polymeric substance, and the weight ratio is 1:10.
An image duplicating material characterized in that the polymer substance contains 0.5 to 10% by weight of a cationic surfactant and a nonionic surfactant in a ratio of ~5:1. 2 Am− between the photosensitive resin layer and the protective layer
Image reproduction material according to claim 1, characterized in that it has a scratch-resistant layer containing a compound represented by Bn. [However, in the above formula, A is monovalent or divalent
an optionally branched aliphatic hydrocarbon having 11 to 20 carbon atoms, B is hydrogen, a hydroxyl group, an amino group,
It is a nitrile group, an aldehyde group, a carboxyl group, an alkyl amide, an alkyl ester, or an ammonium salt of a carboxylic acid, or a salt of a metal of Groups 1 to 3 of the periodic table, m is 1, 2, or 3, and n is 1 or 2. ]