JPH0148533B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an image-formed product that can be reduced in force and a method for producing the same. 2. Description of the Related Art Conventionally, when image-wise exposing a photosensitive material, a mask having an image that is substantially opaque to actinic light has been used. In particular, when manufacturing printing plates, photosensitive materials are often used, and a method is used in which a relief image or a resist image is formed by exposing the material to actinic rays through the above-mentioned mask and then developing it. For this purpose, the image in the mask is required to have high contrast with respect to actinic radiation. For example, it is necessary to have a portion that is highly transparent to actinic light and a portion that is substantially opaque to actinic light. In printing, when printing photographs or the like, it is necessary to create a mask having a halftone image. At this time, the original image is separated into halftone dots using a photographic method. Next, this is converted into an inverted halftone dot image using a second image duplicating material, and in order to obtain a good halftone image, after repeating the contact inversion operation, the obtained halftone dot image is transferred to a mask film. do. Next, a photosensitive plate material is exposed to light through this mask film and subjected to development processing to produce a printing plate having a halftone image. This second image duplicating material is commonly referred to as a "reversing lithographic film." Many studies have been conducted on lithium-ion film for use in such applications. However, although silver halide photosensitive materials have high sensitivity, they have inherent limitations in high contrast and fringe elimination, have a narrow exposure and development latitude, and have problems such as a decrease in optical density when the power is reduced. be. Also,
Since silver halide film is sensitive to visible light, image duplication work must be done in a dark room, and it is not satisfactory in terms of workability and work environment.We would like to have something that allows image duplication work to be done in a bright room. has been done. For this purpose,
Bright room silver halide films have been developed, and although light room workability has been improved, other aspects remain unsolved. Next, we will discuss the important reduction work for "reversing film." When a silver halide lithium film is used as the second image duplication material, a reduction operation is performed to correct tone values and color density. Particularly in the case of primary color plates, once the film is completed, proof printing is performed and color proofing is performed. Correct the film for each color as a result of color proofing. Modification of silver salt lithographic films is carried out by treatment with oxidizing agents. Partial or total correction is performed by removing fog from transparent parts, adjusting the shape of blurred feet, reducing the size of halftone dots, or changing the tone value of halftone dots. This series of operations is called force reduction work. Conversely, making the halftone dots thicker is also done by utilizing this force reduction property. In other words, by reversing a positive film to create a negative film,
Next, when the force is reduced to make it thinner, and this negative film is reversed to make a positive film, halftone dots that are thicker than those of the original positive film are obtained. Recently, an element consisting of a photopolymerizable layer, a protective layer, and a support having an optical density of at least 3 in the active light range has been proposed as a means to reduce costs, solve resource problems, and solve the disadvantages of silver salt films. has been done. (Japanese Patent Publication No. 52-62427) This non-silver salt lithium film has bright room properties, and after image exposure through a mask material, it can be easily developed by washing with water, dipping in alkali, spraying, washing with water, and drying. As a result, a mask film with high contrast and no fringes can be obtained. In addition, the produced mask film has the advantage that it can be easily reduced in strength by treatment with an alkaline aqueous solution and washing with water. However, it has been found that when reducing the force of this non-silver salt film, there are differences in the ability to reduce the force depending on the processing conditions and storage conditions before performing the force reduction operation.
In other words, if the drying temperature is high, the storage conditions are poor, or if it is exposed to indoor light, the strength reducing ability will decrease or the strength will decrease due to the progress of dark reactions, thermal fogging, photopolymerization, crosslinking reactions, etc. becomes incapable. When actually used as a mask film, the finished mask film is used for calibration work. Proofreading work generally involves printing on a photosensitive proofing material or photosensitive plate material, printing a proof, and making a proof. Next, this mask film is corrected. However, due to the exposure of the photosensitive proofing material and photosensitive plate material during printing, photopolymerization and crosslinking reactions progress, and even if you try to reduce the force for correction next time, it will not be possible to reduce the force. It turned out that it has the disadvantage that it disappears. From a practical point of view, this means that the film has lost its force-reducing properties, which is necessary as a "returning film." The inventors of the present invention have conducted intensive studies to maintain excellent force reduction properties regardless of dark reactions, heat fogging, or exposure during handling of the mask film during and after processing, and as a result, they have finally developed the present invention. I have come to complete it. That is, the present invention is formed by image-forming a photosensitive material including a support and a photosensitive layer and removing the easily soluble areas, and the image forming area is composed of a hardened upper layer part and an uncured lower layer part. 1. A reducible image-formed product and a method for producing the same, characterized in that the image-forming area contains an effective amount of a polymerization inhibitor. In the present invention, the expression that the image forming area consists of a hardened upper layer part and an uncured lower layer part means that the degree of polymerization or curing of the image forming area of the photosensitive layer is highest on the surface, and as the layer becomes lower, This indicates that the degree of polymerization or curing is becoming lower. This is achieved by the photosensitive layer having a certain level of absorbance for actinic rays, and after image formation,
This is a necessary condition when reducing power. In addition, in the present invention, the effective amount of the polymerization inhibitor refers to the amount required to maintain the force-reducing property even after image formation and after various conditions such as exposure and long-term standing. However, the effective amount thereof varies depending on the type of polymerization inhibitor described below. Conventionally, a small amount of polymerization inhibitor has been added to the photosensitive layer in advance. Since the amount was small and the ability to inhibit polymerization was lost after exposure in image formation, force reducing properties could not be maintained. On the other hand, if the amount of polymerization inhibitor added in the photosensitive layer is increased in order to maintain the force reducing property, the sensitivity will be significantly lowered and it will be impossible to put it to practical use. The present invention solves the above-mentioned drawbacks, and does not only cause dark reactions and heat fog after exposure, during and after development, but also when exposed to room light or when printed on a photosensitive material. Furthermore, the present invention provides an image-formed product that maintains force-reducing properties. Examples of the support for the image-formed product of the present invention include glass plates, plastic films, glass plates and plastic films having thin layers of metal or metal compounds on their surfaces, metal plates, papers, and the like. Plastic films include polyolefins such as polyethylene and polypropylene, polyvinyl halides such as polyvinyl chloride and polyvinylidene chloride, cellulose derivatives such as cellulose acetate, nitrocellulose, and cellophane, polyamides, polyesters, polystyrene, and polycarbonate. A single film or a laminated film of polyimide or the like is used. Particularly preferred among these is biaxially oriented polyethylene terephthalate film, which has excellent dimensional stability and transparency. The method for providing a thin layer of the metal or metal compound on the surface of glass or plastic film includes:
There are vapor deposition methods, sputtering methods, ionized electrostatic plating methods, plating methods, etc. Aluminum is the most desirable metal to use in terms of ease of handling, cost, toxicity, etc. A subbing layer may be provided on these supports for the purpose of improving adhesion to the photosensitive layer or for other purposes. The photosensitive layer in the image-formed product of the present invention contains a photoinitiator, a monomer, a binder, and an actinic ray absorber as exemplified below, and if necessary, a stabilizer, a plasticizer, a surfactant, and a colorant. etc. are added. 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, benzophenone derivatives such as 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, anthraquinone, 2-chloroanthraquinone, 2ethylanthraquinone, 1-chloroanthraquinone, Aromatic ketones such as phenanthraquinone, benzoin, benzoin alkyl ethers, benzoin derivatives such as α-methylbenzoin, benzyl dimethyl ketal, polynuclear quinones, 2,4,5-triarylimidazole dimer and free There are combination systems of group generators. Furthermore, the sensitivity can be further improved by adding a sensitizer or a sensitizing dye. In addition, examples of the 2,4,5-triarylimidazole dimer include 2-(0-methoxyphenyl)-4,5-diphenylimidazole dimer,
Triphenylimidazole dimers such as 2-(0-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer, 2 -(1-naphthyl)-4,5-diphenylimidazole dimer, 2-(9-anthryl)-
4,5-diphenylimidazole dimer, 2-
(2-methoxy-1-naphthyl)-4,5-diphenylimidazole dimer, 2-(2-chloro-
Examples include polycyclic aryl-4,5-diphenylimidazole dimers such as 1-naphthyl)-4,5-diphenylimidazole dimers. The free radical generator used in combination with the 2,4,5-triarylimidazole dimer includes:
p-aminophenyl ketone compounds such as p,p'-bis(dimethylamino)benzophenone; leucotriphenylmethane dyes such as leucomalachite green and leuco crystal violet; 2.
Cyclic dithitone compounds such as 4-diethyl-1,3-cyclobutanedione, thioketone compounds such as 4′4′-bis(dimethylamino)thiobenzophenone, mercaptan compounds such as 2-mercaptobenzothiazole, N-phenylglycine , dimedone, 7-diethylamino-4-methylcoumarin, and the like. As the sensitizer or sensitizing dye, xanthene-based, acridine-based, thiazine-based, cyanine-based dyes and the like are effective. b Actinic ray absorber By adding, in addition to the photoinitiator, a compound effective in absorbing actinic rays, an image that is opaque to actinic rays can be formed. By increasing the absorption of actinic rays, only the upper layer of the image exposed through the transparent portion of the mask undergoes a curing reaction, while the lower layer remains uncured. In this way, if the uncured lower layer can be maintained, the force-reducing properties can be maintained. On the other hand, if the absorption amount of actinic rays is small, even the lower layer will be hardened during exposure, making it impossible to reduce the force later. Furthermore, if the amount of actinic rays absorbed is too large, only the very thin upper layer can be cured, resulting in not only poor resist effect but also poor photosensitivity. The most preferable photosensitive layer has an actinic ray absorbance of 2 to 4. Actinic light absorbers used include ultraviolet absorbers, ultraviolet absorbing dyes, and other dyes and pigments. Examples of these are carbon black,
Titanium oxide, iron oxide, various metals and metal oxides,
Powder of compounds such as sulfides, pigment black (CI50440), chrome yellow light (C.
I.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.
I.71680), Molybdenum Orange (CI77605), Sudan Yellow (CI30), Oil Orange (C.
I.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, metal compounds, etc., it is necessary to make them into fine particles by physical or chemical methods. c Monomer The monomer used may have one or more polymerizable double bonds. Examples of such compounds include hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate,
Alkyl acrylate or alkyl methacrylates such as benzyl acrylate and benzyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate,
NN-Dialkylaminoalkyl acrylates or methacrylates, alkyl ether acrylates or methacrylates such as methoxyethyl acrylate, ethoxyethyl methacrylate, halogenated alkyl acrylates or methacrylates, alkyl acrylics or methacrylamides, hydroxyalkyl acrylates or methacrylates acrylates or methacrylates of polyalkyl ethers such as diethylene glycol diacrylate or methacrylate, triethylene glycol diacrylate or methacrylate, ethylene glycol diacrylate or dimethacrylate, polyvalents such as glycerin, trimethylolpropane, pentaerythritol Alcohol acrylates or methacrylates, acrylic acid,
A reaction product of methacrylic acid, glycidyl acrylate or methacrylate with an active hydrogen-containing substance,
Examples include reaction products of glycidyl compounds and acrylic acid or methacrylic acid, condensates of N-methylol compounds and urea compounds, and reaction products of polyisocyanate compounds and hydroxyalkyl acrylates or methacrylates. The monomer used is 1
The monomers to be used need to be selected depending on the type of binder, the ratio of monomers, the type and amount of photoinitiator, the type and amount of actinic light absorbing compound, etc. Yes, determined based on compatibility, film-forming properties, stability, photosensitivity, etc. If the monomer used has a low boiling point, it will volatilize and decrease during or after film formation, so a higher boiling point is desirable. d Binder The binder must be an organic polymer that is soluble in a solvent, solid at temperatures below 50°C, and compatible with the 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, their coexisting derivatives (cellulose ethyl ether, cellulose acetate, carboxymethyl cellulose, cellulose acetate succinate, cellulose methyl ether phthalate, cellulose methyl ether succinate, etc.), and polyesters. Alkyl ethers, polyesters, polyamides, polyvinyl esters and their copolymers, phenolic resins, polyvinylidene compounds, polyvinyl alcohols, gelatin and its derivatives, polyvinyl butyral, polyacrylamide, polyvinylpyrrolidone, polystyrene, chlorinated rubber, Examples include polyethyleneimine. 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, and polymers containing carboxyl groups quaternized with acid in tertiary nitrogen-containing polymers;
Examples include polyvinylpyrrolidone and polyethyleneimine. 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, itaconic acid, and crotonic acid. Examples include copolymers of vinyl monomers, polyesters containing tertiary nitrogen groups, polyamides, and vinyl polymers. Note that the main chain or side chain of the binder may contain a polymerizable unsaturated double bond group. From the support and photosensitive layer listed above, the photosensitive material used in the present invention can be obtained by a conventional method. Next, as a method for obtaining an image-formed product of the present invention, 1. After imagewise exposing a photosensitive material including a support and a photosensitive layer, and before removing the easily soluble portion, the photosensitive material is exposed to a polymerization inhibitor and/or a solution containing a polymerization inhibitor. Method of immersion treatment. 2. When imagewise exposing a photosensitive material including a support and a photosensitive layer and removing easily soluble areas using a developer,
A method in which a polymerization inhibitor is added to the developer and processing is performed simultaneously with development. 3. A method of imagewise exposing a photosensitive material including a support and a photosensitive layer, and immersing an image formed product obtained by removing an easily soluble area in a polymerization inhibitor and/or a solution containing the polymerization inhibitor. and so on. Examples of the polymerization inhibitor used in the method of the present invention include p-benzoquinone, naphthoquinone, paraxyquinone, paratoluquinone, 2,6
- Quinones such as dichloroquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-diacyloxy-p-benzoquinone, hydroquinone, pt-butylcatechol, mono-t-butylhydroquinone,
Hydroquinones such as 2,5-di-t-amylhydroquinone, phenols such as hydroquinone monomethyl ether, amidines such as acetamidine acetate and acetamidine sulfate, hydrazine salts such as phenylhydrazine hydrochloride and hydrazine hydrochloride, Quaternary ammonium salts such as trimethylbenzylammonium chloride and cetyltrimethylammonium chloride, amines such as phenyl-β-naphthylamine, p-benzylaminophenol, di-β-naphthylparaphenylenediamine, nitrobenzene,
Nitro compounds such as trinitrotoluene and picric acid, oximes such as quinone dioxime and cyclohexanone oxime, polyhydric phenols such as pyrogallol, tannic acid, and resorcinol, triethylamine hydrochloride, dimethylamine hydrochloride, dibutylamine hydrochloride, etc. Examples include amine hydrochlorides, organic and inorganic copper salts such as copper naphthenate, nitroso compounds such as nitrosobenzene, nitroso-β-naphthol, and cuperone, and dyes having polymerization inhibiting ability. Used together. The polymerization inhibitor may be simply physically adsorbed or fixed to the image forming area, or may be caused by a chemical reaction. It is desirable that the boiling point is high enough to not volatilize and disappear. Further, it is not preferable that the polymerization inhibitor deteriorates in quality and its ability to inhibit polymerization decreases. From the viewpoint of ease of processing, it is preferable to use one that can be easily processed for a short time, satisfies the above requirements, is non-toxic, and is inexpensive. Particularly in the case of solution processing, organic solvents are undesirable in terms of handling costs and the like. Particularly preferred are those that can be used in the form of an aqueous solution or aqueous dispersion. This compound is hydroquinone. Further, for the purpose of improving processing performance, auxiliary agents such as surfactants may be used. In the above method, an aqueous solution of hydroxides and carbonates of alkali metals such as lithium, sodium, and potassium is used as a developer for removing easily soluble areas after image exposure, and particularly preferred are sodium hydroxide, It is an aqueous solution of sodium carbonate, potassium hydroxide, potassium carbonate, etc. Further, as the acidic aqueous developer, an aqueous solution of an inorganic or organic acid such as hydrochloric acid, formic acid, or oxalic acid can be used, and neutral water can also be used. The polymerization inhibitor contained in the image forming area of the image-formed product of the present invention obtained by any of the above methods must have an effective amount, that is, an amount to maintain force-reducing properties. varies depending on the type of polymerization inhibitor, and the conditions in the method, such as immersion time, are appropriately determined so that an effective amount of the polymerization inhibitor is contained. The image-formed product of the present invention having the above-mentioned structure solves the problem of loss of force reducing property, which was considered to be a drawback of conventional non-silver salt lithium films, by a simple method,
After image formation, the film retains its strength-reducing properties under various conditions, making it the first non-silver salt lithium film available on the market. EXAMPLES Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto. 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 A photosensitive composition was prepared by mixing and dispersing the components, and it was coated on the polyester film provided with the above-mentioned undercoat layer using a reverse coater to form a photosensitive layer having a thickness of 4 μm. Copolymer of methyl methacrylate (70 mol%) and methacrylic acid (30 mol%) 41 parts carbon black 12 parts trimethylolpropane triacrylate 34 parts 2-(2-chloro-1-naphthyl) 4,5- Diphenylimidazole dimer 8 parts Hydroquinone monomethyl ether 0.03 parts Dimedone 3 parts 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, the following composition was printed on this film. The composition for the protective layer is coated in the same manner, and the thickness
A photosensitive film with a protective layer of 1μ was prepared. Polyvinyl alcohol 5 parts (saponification degree 98.5%, polymerization degree 500) Neugen EA-140 (Daiichi Kogyo Seiyaku) 0.2 parts methanol 5 parts water 90 parts company) and 150l/in, 5 to 95
% halftone dots were stacked on top of each other, and image exposure was performed for 20 seconds using a bright room printer (manufactured by ORC). Next, after removing the protective layer by washing with water, it was placed in a 1% Na ₂ CO ₃ aqueous solution adjusted to 30℃.
After immersing for 10 seconds, washing with water, developing and drying while rubbing with a sponge, a reversed image was obtained. It was found that up to the 5th step of the step guide was hardened, and the halftone dots reproduced the negative well. Next, the duplicate halftone image made in the same manner was immersed in a 5% aqueous solution of hydroquinone kept at 30℃ for 10 seconds and 20 minutes.
After being immersed for 2 seconds, 30 seconds, and 60 seconds, the samples were washed with water and dried. The thus treated and untreated samples were left indoors (at 800 lux during the day), and changes in force reduction over time were measured. The reduction force is 20℃,
This was done by immersing the sample in an aqueous solution containing 5% NaCO ₃ and 0.1% Neugen EA-140 for 60 seconds, and then rubbing with a sponge while rinsing with water. The results are shown below.

[Table] As is clear from the above results, by using the method of the present invention, it was possible to suppress the decrease in force reduction properties due to the progress of the reaction when left indoors. In comparison, it can be seen that in the case of the comparative example (untreated), the force reducing ability significantly decreases after being left for several days, making it impossible to reduce force. Example 2 A halftone image produced in the same manner as in Example 1 was immersed in an aqueous solution containing 4% hydroquinone and 0.2% Neugen EA-140 for 60 seconds, washed with water, and dried. This halftone image is used as a negative film to create a negative PS version.
Printing was carried out on SGN- (manufactured by Fuji Photo Film) using a 2K.W. mercury lamp (manufactured by ORC).
Next, when this negative film was reduced in force in the same manner as in Example 1, it was found that it had a force reduction property of 28%. However, when a similar test was conducted using untreated negative film, 2%
I was becoming unable to reduce my strength. Example 3 The photosensitive film obtained in Example 1 was image-exposed using a test negative, the protective layer was removed by washing with water, and then 4% of hydroquinone, 1% of Na ₂ SO ₃ ,
After immersing it in an aqueous solution containing 0.3% Na ₂ CO ₃ for 45 seconds, it was washed with water and developed by rubbing with a sponge. The resulting treated film maintained 24% strength reduction from the base side even after exposure for 30 seconds in a bright room printer. On the other hand, when the same treatment was carried out without adding hydroquinone, there was almost no reduction in strength. Example 4 The photosensitive film obtained in Example 1 was subjected to image exposure using a test negative, and then the protective layer was removed by washing with water.
And hydroquinone 4% and Neugen EA-140
It was immersed in an aqueous solution containing 0.4% for 3 minutes. Next, the film was immersed in 1% NA ₂ CO ₃ for 8 seconds, washed with water, developed with a sponge, and dried. The obtained film was exposed from the base side using a bright room printer in the same way as in Example 3.
It was found that it maintains a force reduction of 20%. In contrast, those that were not treated with a hydroquinone solution had only a 2% reduction in strength.

Claims (1)

[Scope of Claims] 1. Obtained by imagewise exposing a photosensitive material including a support and a photosensitive layer and removing easily soluble areas, the image forming area is formed from a hardened upper layer part and an uncured lower layer part. 1. An image-formed product which can be reduced in force, characterized in that the image-forming area contains an effective amount of a polymerization inhibitor. 2. After imagewise exposing the photosensitive material including the support and the photosensitive layer, before removing the easily soluble parts, it is subjected to immersion treatment in a polymerization inhibitor and/or a solution containing the polymerization inhibitor. A method for producing an image-formed product. 3. A method for producing an image-formed product that can be reduced in strength, which comprises imagewise exposing a photosensitive material including a support and a photosensitive layer, and then removing easily soluble areas using a developer containing a polymerization inhibitor. 4. Imagewise exposing the photosensitive material including the support and the photosensitive layer, and immersing the image formed product obtained by removing the easily soluble area in a polymerization inhibitor and/or a solution containing the polymerization inhibitor. A method for producing an image-formed product capable of reducing force, characterized by: