JPH0119573B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel photosensitive resin composition, and more specifically, the degree of hydrophilicity of a photosensitive compound,
Or it relates to a photosensitive resin composition using a method of photochemically changing its solubility in water. In recent years, with the increase in the amount of information, the demand for photosensitive materials has increased in various fields, and it is well known that research on new photosensitive materials to meet this demand has been actively conducted. Performance requirements for these new photosensitive materials, such as resolving power, photosensitive speed, shelf life, and ease of processing, are becoming increasingly strict. As a result of extensive research under these circumstances, the present inventors have developed a photosensitive resin composition that has new characteristics different from conventional photosensitive materials as disclosed in JP-A No. 55-98744. succeeded in obtaining it. This composition has a large difference in water insolubility and water solubility upon irradiation with light, high resolution, possibility of corrective erasure of an image once obtained, and a thin film state in which oxygen molecules easily diffuse from the air. stability of the reaction rate,
Because it has excellent features such as an extremely long shelf life, it can be applied in many fields. However, the photoreaction rate was rather slow, which caused problems in practical use. Therefore, the present inventors conducted extensive research on a new highly sensitive photosensitive resin composition that has the above-mentioned various characteristics and further exhibits a high photoreaction rate, and as a result, completed the present invention. In other words, the present invention provides (1) a compound that has low hydrophilicity or is water-insoluble by itself, but becomes highly hydrophilic or water-soluble due to acid-base interaction in the coexistence with an acidic compound; at least one basic polymer compound having similar properties, and (2)
The following general formulas ()-a, ()-b, ()-c,
A photosensitive resin composition characterized by containing at least one of the acidic compounds represented by () and (). [Wherein, X is nitrogen, oxygen, sulfur, selenium, R ₁ ,
R ₂ is hydrogen, an alkyl group having 1 to 6 carbon atoms with or without a substituent, a phenyl group, R ₅
is hydrogen, carbon number 1-6 with or without substituents
n is 0 or 1, m is 1 when X is nitrogen, and 0 when X is oxygen, sulfur, or selenium. ] [Wherein, Y is NR ₈ , sulfur, R ₇ and R ₈
each represents H and an alkyl group having 1 to 3 carbon atoms. ] [In the formula, Z is oxygen or sulfur, R ₉ is a phenyl group with or without a substituent, and k is 0 or 1
shows. ] In the present invention, the acidic compounds represented by the general formulas () to () are originally acidic, and when exposed to light, undergo a chemical change and lose their acidity, or
Or, it is a compound whose acid-base interaction with the basic polymer compound of (1) is eliminated by light irradiation in the coexistence with the polymer compound, and in the general formula ()-a, , R ₁ and R ₂ include halogen, hydroxyl group, lower alkyl group, nitro group, cyano group, alkylcarbonyl group, alkoxy group, N-substituted carbamoyl group, N-substituted sulfamoyl group, and the like. Also R ₅ , R ₆
Examples of the substituents included in this group include a hydroxyl group, an imidazolyl group, and an aminocarbonyl group. Specific examples of compounds represented by general formulas ()-a to ()-c include N-phenylglycine, N-(3-
chlorophenyl)glycine, N-(2,4-dichlorophenyl)glycine, N-(4-acetylphenyl)glycine, N-(2-nitrophenyl)
Glycine, N-(4-nitrophenyl)glycine,
N-(2,4-dinitrophenyl)glycine, N
-(4-cyanophenyl)glycine, N-(3-chlorophenyl)glycine, N-(2-bromophenyl)glycine, N-(2-methylphenyl)glycine, N-(2-methoxyphenyl)glycine,
N-(2-methoxyphenyl)glycine, N-
(2,4-dimethoxyphenyl)glycine, N-
Methyl-N-phenylglycine, N-methyl-N
-(2-methylphenyl)glycine, N-methyl-N-(4-chlorophenyl)glycine, N-methyl-N-(2-nitrophenyl)glycine, N
-Methyl-N-(2-methoxyphenyl)glycine, N-(2-carbamoylphenyl)glycine,
N-(4-sulfamoylphenyl)glycine,
N-phenylalanine, N-phenylserine, N
-Phenylhistidine, N-phenylasparagine, N-phenylglutamine, N-carboxymethylcarbazole, 3-anilino-2-propene-1-carboxylic acid, indole-3-acetic acid, phenoxyacetic acid, 2-methylphenoxyacetic acid, (3-
methoxyphenoxy)acetic acid, (2-nitrophenoxy)acetic acid, (3-chlorophenoxy)acetic acid, (4
-methylphenoxyacetic acid, thiophenoxyacetic acid, 3-methoxythiophenoxyacetic acid, 2-chlorothiophenoxyacetic acid, 2-methylthiophenoxyacetic acid, 4-nitrothiophenoxyacetic acid, S-hydroxyethylthioacetic acid, Examples include S-n-butylthioacetic acid and phenylcarboxymethylselenide. Specific examples of the compound represented by the general formula () include indoxylic acid, 4-nitroindoxylic acid, thioindoxylic acid, N-methylindoxylic acid, and the like. Next, in the general formula (), the substituents for _R10 include halogen, nitro group, alkoxy group,
Examples of compounds represented by the general formula () include benzoyl formate, 2-chlorobenzoyl formate, 4-chlorobenzoyl formate, N-dimethylaminobenzoyl formate, thiobenzoyl formate, and benzoyl formate. acetic acid,
Examples include thiobenzoyl acetic acid. The basic polymer compound used in the present invention is one in which the monomer forming the polymer compound has a group showing basicity, and the basic group has a pka of 2 or more as measured by potentiometric titration in an aqueous solvent system. What you show is what you say.
Manufactured by general polymerization reactions such as polycondensation and polyaddition reactions using monomers having a basic group in the molecule as exemplified below and other monomers if necessary. It includes a polymer compound, or a modified polymer compound obtained by imparting basicity to a synthetic polymer compound or a natural polymer compound by chemical modification. Such polymers may be not only homopolymers but also random copolymers or block copolymers. Examples of the basic polymer compound used in the present invention include those having a basic nitrogen atom,
In this case, the nitrogen content in the polymer compound is 0.1-25
Equivalents/Kg, particularly preferably 0.1 to 14 equivalents/Kg. Examples of basic polyamides include those using monomers represented by the following general formulas () to () as polymerization raw materials: [In the formula, R, R' are hydrogen or hydrocarbon residues having 1 to 10 carbon atoms; R'', R are hydrocarbon residues having 1 to 10 carbon atoms; R ₁₁ , R ₁₂ , and R ₁₃ are hydrogen residues having 1 to 10 carbon atoms; ~15 alkylene group; R ₁₄ and R ₁₅ represent a hydrocarbon acid group having 1 to 10 carbon atoms, and R ₁₄ and R ₁₅ may jointly form a ring or a heterocyclic ring. R ₁₆ is a carbon lower alkyl group of numbers 1 to 3 or

[Formula] (where R ₁₄ and R ₁₅ have the same meanings as above). In addition, A and B are groups selected from the group consisting of -NH ₂ , -COOH, -COOR′′′′ (where R′′′′ represents a hydrocarbon residue having 1 to 10 carbon atoms). A and B may be the same or different at the same time. Moreover, Y represents a 3-aminopropyl group. ] As the monomer represented by the above general formula (),
N-(2-aminoethyl)piperazine, N-(4-
aminocyclohexyl)piperazine, N-(2-
Diamines such as (aminoethyl)-3-methylpiverazine, N-carboxymethylpiperazine, N
-(4-carboxycyclohexyl)piperazine,
Examples include ω-amino acids such as N-(2-carboxyethyl)-3-methylpiperazine, and lower alkyl esters thereof. Examples of the monomer represented by the general formula () include N,N'-bis(aminomethyl)piperazine,
N-(aminomethyl)-N'-(2-aminoethyl)
Diamines such as piperazine, N,N'-bis(carboxymethyl)piperazine, N,N'-bis(carboxymethyl)-2,6-dimethylpiperazine, N-(2-carboxyethyl)-N'-(carboxy Dicarboxylic acids such as (methyl)piperazine or their lower alkyl esters, acid halides, and N-(aminomethyl)-N'-(carboxymethyl)piperazine, N-(aminomethyl)
Examples include ω-amino acids such as -N'-(carboxymethyl)-2-methylpiperazine, and lower alkyl esters thereof. Examples of the monomer represented by the general formula () include N,N-bis(2-aminoethyl)-methylamine, N,N-bis(3-aminopropyl)-
Diamines such as cyclohexylamine, N,N
-bis(carboxymethyl)-methylamine, N
-Dicarboxylic acids such as carboxymethyl-N-(2-carboxyethyl)-methylamine or their lower alkyl esters, acid halides, and N-(aminomethyl)-N-(carboxymethyl)-methylamine, N- (aminomethyl)
Examples include ω-amino acids such as -N-(2-carboxyethyl)-isopropylamine, and lower alkyl esters thereof. Examples of monomers represented by the general formula () include N,N'-dimethyl-N,N'-bis(3-aminopropyl)ethylenediamine, N,N'-dicyclohexyl-N,N'-bis(3-aminopropyl) -aminopropyl)hexamethylenediamine, N,N'-dimethyl-N,N'-bis(carboxymethyl)ethylenediamine, N,N'-dimethyl-N,N'-bis(3-carboxypropyl)
Dicarboxylic acids such as hexamethylene diamine or their lower alkyl esters, acid halides, N,N'-dimethyl-N-(aminomethyl)-N'-(carboxymethyl)ethylenediamine, N,N'-dimethyl-N- (aminomethyl)-
Examples include ω-aminos such as N'-(carboxyethyl)hexamethylene diamine, and lower alkyl esters thereof. Examples of the monomer represented by the general formula () include 6-methyl-6-(N,N-dimethylaminomethyl)-4,8-dioxa-1,11-undecanediamine, 6-ethyl-6-( N,N-dimethylaminomethyl)-4,8-dioxa-1,11-
undecanediamine, 6,6-bis(N,N-dimethylaminomethyl)-4,8-dioxa-1,
There are diamines such as 11-undecanediamine. Two or more of these basic monomers may be used in combination. In addition to the monomers represented by the general formulas () to () above, the polymerization components of the polyamide used in the present invention include aliphatic and/or aromatic dicarboxylic acids, diamines, and -Amino acids, lactams, etc. Examples of basic polyesters include those using monomers represented by the following general formulas () to (XII) as polymerization raw materials: [In the formula, R, R′, R″, R, R ₁₁ , R ₁₂ , R ₁₃ ,
R ₁₄ , R ₁₅ , and R ₁₆ have the same meanings as above. A′, B′ are −OH,
-COOH, -COOR′′′′ (where R′′′′ is 1 carbon number
~
The 10 hydrocarbon residues are shown. ), and A' and B' may be the same or different at the same time. ]. As the monomer represented by the above general formula (),
Specifically, N,N'-bis(carboxymethyl)
Piperazine, N,N'-bis(carboxymethyl)
Dicarboxylic acids such as -2,6-dimethylpiperazine, N-(2-carboxyethyl)-N'-(carboxymethyl)piperazine, or their lower alkyl esters, acid halides, N,
N'-bis(hydroxymethyl)piperazine, N,
N'-bis(2-hydroxypropyl)-2,5-
Dimethylpiperazine, N,N'-bis(2-hydroxycycloheptyl)piperazine, N,N'-
Glycols such as bis(2-methyl-2-hydroxynonyl)piperazine can be mentioned. Examples of monomers represented by the general formula () include dicarboxylic acids such as N,N'-bis(carboxymethyl)-methylamine and N-carboxymethyl-N-(2-carboxyethyl)-methylamine; lower alkyl esters, acid halides, and glycols such as N,N-bis(2-hydroxyethyl)amine and N,N-bis(2-hydroxypropyl)-isopropylamine. Examples of the monomer represented by general formula (XI) include N,N'-dimethyl-N,N'-bis(carboxymethyl)ethylenediamine, N,N'-dimethyl-N,N'-bis(3- carboxypropyl)
Dicarboxylic acids such as hexamethylene diamine or their lower alkyl esters, acid halides, N,N'-dimethyl-N,N'-bis(2
-hydroxyethyl)ethylenediamine, N,
N'-dicyclohexyl-N,N'-bis(2-hydroxyethyl)hexamethylenediamine, N,
There are glycols such as N'-dimethyl-N,N'-bis(2-hydroxyethyl)-2,2,4-trimethyl-hexamethylenediamine. Examples of the monomer represented by general formula (XII) include 2-methyl-2-(N,N'-dimethylaminomethyl)-1,3-propanediol, 2-methyl-2-(N,N- diisopropylaminomethyl)
-1,3-propanediol, 2-methyl-2-
piperidinomethyl-1,3-propanediol,
Examples include glycols such as bis(2-N,N-diisopropylaminomethyl)-1,3-propanediol. Two or more of these basic monomers may be used in combination. In addition to the monomers represented by the general formulas () to (XII), the raw materials for polymerization of the polyester used in the present invention include aliphatic and/or aromatic dicarboxylic acids or their lower Alkyl esters, glycols, oxyacids, etc. may be used in combination. As a vinyl polymer having basicity, 4
- Polymer of vinylpyridine, or the following general formula (): [In the formula, R′, R″, R, and R ₁₁ have the same meanings as above.Q
represents an ester bond or an amide bond. ] Those using monomers shown in the following as polymerization raw materials are mentioned. Examples of the monomer represented by the above general formula () include 2-(N,N-dimethylamino)ethyl methacrylate, 3-(N,N-diethyl)
Methacrylates such as propyl methacrylate, 3-(N,N-dimethylamino)propyl methacrylamide, 3-(N,N-diethylamino)
Examples include methacrylamides such as propyl methacrylamide. Two or more of these basic monomers may be used in combination. As a polymerization raw material for the vinyl polymer used in the present invention, in addition to the above-mentioned 4-vinylpyridine or the monomer represented by the general formula (), a vinyl monomer used in the polymerization of ordinary vinyl polymers may be used in combination. . As the polyether having basicity, a diol having basicity, for example, the above general formula ()
There are those obtained by polycondensation from the diols represented by these or their functional derivatives, and those obtained by polycondensation with other diols or their functional derivatives. Other diols or functional derivatives thereof include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, molecular weight 200
-3000, preferably 200-1000 polyethylene glycol, polytetramethylene glycol, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane,
bis(4-hydroxyphenyl)thioether,
Bis(4-hydroxyphenyl)sulfone, 2,
2'-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
Cresol, resorcinol, hydroquinone, 2,4
-dihydroxyacetophenone, 1,5-dihydroxynaphthalene, p-, m- or o-xylylene glycol, and the like. The above polyether is produced by polycondensation according to a conventional method. Examples of modified polymer compounds include cellulose derivatives modified with ethyleneamine, such as aminoethyl cellulose, and modified polymers that have been given basicity by a graft reaction, which is known as a general modification method for polymer compounds. Examples include molecular compounds. Furthermore, in the composition of the present invention, in addition to the basic polymer compound, other kinds of polymer compounds can also be used in combination. The basic polymer compound and the general formula ()-a,
The amount and mixing ratio of the acidic compounds represented by ()-b, ()-c, () and () in the composition vary depending on the type of combination of the two, and the characteristics required during actual use. (For example, the difference in hydrophilicity or water solubility before and after light irradiation, mechanical properties, reaction rate, etc.)
It is preferable that the proportion of both is such that the equivalent ratio of the acidic group of the acidic compound to the basic nitrogen contained in the basic polymer compound is 0.02 to 1. The composition of the present invention includes the general formula ()-a,
In addition to the acidic compounds shown in ()-b, ()-c, () and (), if necessary, acidic compounds that do not lose their acidity even when exposed to light are used in combination before and after light irradiation. It is also possible to control differences in the hydrophilicity or water solubility of. Furthermore, it is of course possible to use a conventionally known photoinsolubilizing agent in combination for the same purpose and to control mechanical properties. Examples of photoinsolubilizers that can be used in combination include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, cyclohexyl acrylate, acrylamide, methacrylamide, N-methylolacrylamide, n-butoxymethylacrylamide, sodium acrylate, ammonium acrylate, acrylonitrile, styrene, Monomers with one unsaturated double bond such as sodium styrene sulfonate and vinylpyridine, or glycidyl methacrylate, allyl methacrylate, ethylene glycol di(meth)acrylate, 1,3-propanediol(meth)acrylate, and trimethylol There are monomers having two or more unsaturated double bonds, such as propane tri(meth)acrylate, triacryloyloxyethyl phosphate, and methylenebis(meth)acrylamide. In the composition of the present invention, sensitivity may be increased by further adding a photosensitizer. Examples of the photosensitizer used in the present invention include 4,
Aromatic ketone compounds such as 4'-bisdimethylaminobenzophenone, thioxanthone, fluorenone, trinitrofluorenone, aromatic thioketone compounds such as 4,4'-bisdimethylaminothiobenzophenone, benzoquinone, dichlorobenzoquinone, Quinone compounds such as tetrachlorobenzoquinone, dichlornaphthoquinone, phenanthrenequinone, dichloroanthraquinone, dinitroanthraquinone, alizarin, benzanthraquinone, dinitrofluorene, tetranitrofluorene, trinitrofluorene, nitroacenaphthene, 2,4,6 - Aromatic nitro compounds such as trinitroaniline, triarylpyrazoline compounds such as triphenylpyrazoline, monoimidazole compounds such as tetraphenylimidazole and triphenylimidazole, fluorescein,
Eosin Y, Rose Bengal, Erythrosin B,
These include xanthene compounds such as phloxine, acridine compounds such as acriflavin and riboflavin, coumarin compounds such as 7-N-dimethylaminocoumarin, and triphenylmethane compounds such as thymol blue, bromthymol blue, and bromcresol green. Among these, aromatic ketone compounds, quinone compounds, aromatic nitro compounds, triarylpyrazoline compounds, and coumarin compounds are preferred. The photosensitizer is preferably added in an amount of 0.1 to 1% by weight, particularly 0.1 to 5.0% by weight, based on the total composition. In preparing the composition of the present invention, both a basic compound and an acidic compound represented by general formulas () to () are dissolved in an appropriate solvent and mixed uniformly,
A method of forming acid-base pairs between the two is adopted.
Suitable solvents include lower alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, esters such as methyl cellosolve and ethyl cellosolve, aromatic compounds such as toluene and xylene, or two or more of these. Mixtures can be used. However, if the basic polymer compound used is liquid at room temperature or has a relatively low melting point, softening point, or pour point, a method of directly mixing the two without using a solvent may also be adopted. The composition of the present invention prepared in this way can be formed into a membrane, film, or film of a desired thickness by, for example, a solution casting method, a hot press method, a casting method, a melt extrusion method, etc.
It can be made into a sheet-like material. Further, these can be laminated on a support with or without an adhesive layer. As the support, any material such as steel, aluminum, plestic film, glass, etc. can be used. Preferred light sources for the composition of the present invention include those rich in light having a wavelength of 400 mμ or less, such as various mercury lamps, carbon arc lamps, xenon lamps, and ultraviolet fluorescent lamps. The composition of the present invention is irradiated with light from these light sources through a so-called negative film or positive film having a desired image or pattern image consisting of a light-transmitting part and a light-blocking part. Alternatively, it is carried out by scanning the surface of the composition of the present invention with a light beam from such a light source in the form of a locus of a desired image or pattern image. The latent image that is first formed on the surface of the composition of the present invention by light irradiation has decreased hydrophilicity or has changed to almost hydrophobicity compared to the area that has not received light irradiation. This can also be expressed as the polarity of the light-irradiated portion being lower than that of the non-irradiated portion. The image latent image or pattern latent image with different polarities obtained on one surface can be used as is without any additional processing, or can be used after being subjected to some development processing. . When the development process requires a solvent, the solvent can be selected arbitrarily depending on the polarity difference between the light-irradiated portion and the non-irradiated portion. Although the use of water is generally most convenient and preferred, water development can be employed with the compositions of the present invention. in this case,
Preferably, water with a pH of 5.5 to 7.5 is used. As mentioned above, the effective use of the composition of the present invention is as follows.
It is mainly formed in relatively thin layers such as membranes, films or sheets, and is often used as a laminate with a suitable support. In terms of specific uses, there are cases where the difference in polarity or hydrophilicity obtained by irradiating the surface of a layered material with light is utilized without changing the form of the layered material, and cases where etching or washout operations with water are used. It may be used in addition. Examples of the former use include electrophotography and electrostatic printing that take advantage of the difference in conductivity that inevitably arises from the difference in polarity, and also as image recording materials that take advantage of the difference in dyeability. On the other hand, the latter is used as various negative resists and for offset printing plates, and as a relief, resin plates for letterpress printing,
Examples of uses include name plates, resin molds for molds, and resin molds for embossing. The compositions of the present invention may also be used in systems premixed with dyes or pigments, providing materials that are also effective in various masking applications for patterned shading. The feature of the composition of the present invention having the above configuration is that its main components are two types of compounds (a polymeric compound having basicity and a general formula () to () that loses acidity upon irradiation with light). By combining selected types of acidic compounds (acidic compounds) and their mutual amount ratios over a wide range, it is possible to express desired performance changes ranging from a very slight change in hydrophilicity due to light irradiation to a large change in water insolubility to water solubility. It's about getting. Furthermore, since the photoreaction of the composition of the present invention does not proceed through a chain reaction, the resolution is extremely high.In other words, unlike the three-dimensional reaction of resins, the composition of the present invention There is no volumetric shrinkage, that is, no image distortion, and therefore high resolution can be maintained. In addition, since non-three-dimensional polymeric compounds are essentially solvent-soluble, when producing, for example, resist images or relief images using the compounds of the present invention, the images once obtained can be corrected and erased. becomes possible. Furthermore, since the photoreaction of the composition of the present invention is not hindered by oxygen unlike the photopolymerization reaction, there is no problem with the reaction rate in a thin film state where oxygen molecules tend to diffuse from the air. will not occur. In addition, thermal stability is high, and the composition of the present invention is guaranteed to have an extremely long shelf life. Another feature of the composition of the present invention is that simple water can be used for etching or washout when obtaining resist images or relief images. This promises a particularly favorable working environment and operability in terms of safety. Furthermore, the composition of the present invention has a fast photoreaction rate and high sensitivity, so it can be sufficiently marketed. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. In the examples, parts represent parts by weight unless otherwise specified. Examples 1-6, Comparative Examples 1-2 2-methyl-2-(N,N-dimethylamino)
One part of a polyester obtained by direct polymerization from methyl-13-propanediol and terephthalic acid and a predetermined amount of the acidic compound shown in Table 1 were each dissolved in methyl ethyl ketone. The resulting solution was applied uniformly to a thickness of 2 μm on each anodized aluminum plate with a thickness of 200 μm.
It was dried with warm air at ℃ for 5 minutes. Next, a negative original film was attached to each sheet and exposed to a high-pressure mercury lamp (Polymer Printer 3000, manufactured by Oak Co., Ltd.) for 2 minutes, 5 minutes, and 10 minutes, respectively. After exposure, each photosensitive plate was immersed in water at 20℃ and pH=7, developed with a washer (manufactured by Dainippon Screen Co., Ltd.), washed with water, drained, and then gummed with a gum solution (GU, manufactured by Fujifilm). and air-dried at room temperature. Table 1 shows the appearance of each printing plate obtained by the above method and the results of printing on a Ryobi KR480 offset printing machine (manufactured by Ryobi Co., Ltd.).

[Table] A in Table 1: A clear continuous tone image with good resolution was obtained. B: Fine points, halftone dots, and independent points were partially missing, and a satisfactory image could not be obtained. C: Thin lines, halftone dots, and independent points were skipped, and the image did not appear in some areas. ○: A clear printed matter that reproduced the original image well was obtained. Δ: Fine lines, halftone dots, and independent points were partially missing, and the original image could not be reproduced satisfactorily. ×: Thin lines, halftone dots, and independent dots were skipped, and the ink receptivity was poor, and a satisfactory printed matter could not be obtained. As is clear from Table 1, the photoreaction rate of Comparative Examples 1 and 2 was slow and unsatisfactory from the practical point of view, but the composition of the present invention has high sensitivity and clear printed matter. I was able to get Example 7 100 parts of a polyamide obtained by polycondensing 40 parts of N-(β-aminoethyl)piperazine, 50 parts of adipic acid, and 38 parts of ε-caprolactam and 50 parts of N-carboxymethylcarbazole were completely condensed using methanol as a solvent. were dissolved and mixed. This solution was coated uniformly to a thickness of 1μ on a 200μ thick anodized aluminum plate, and heated to 50℃ for 2 hours.
Dry with hot air for a minute. A negative original film was adhered to the photosensitive plate and exposed to a 3K.W. ultra-high pressure mercury lamp for 4 minutes. After exposure, the photosensitive plate was immersed in PH7 water at 20°C and washed with a washer (manufactured by Dainippon Screen Co., Ltd.).
After brushing, washing with water and draining water, store at 60℃.
The film was dried in a hot air dryer for 10 minutes, and then gummed with a gum solution (FUJIFILM Corporation: GU).
After drying with room temperature air, use an offset printing machine (manufactured by Ryobi Co., Ltd.)
As a result of a printing test using the KR480 model, a good printed sample with good ink receptivity was obtained.
The halftone dot resolution was 150 lines/inch or more. Example 8 In Example 7, N-phenylalanine 0.6 was used instead of the organic compound N-carboxymethylcarbazole.
A photosensitive plate was obtained in the same manner. A negative original film was closely attached to this photosensitive plate, and Example 7
As a result of carrying out the same operations as in Example 7 and performing a printing test, the same results as in Example 7 were obtained. Example 9 In Example 8, 0.4 phenylcarboxylmethylselenide was used instead of the organic compound N-phenylalanine.
A homogeneous solution of the resin composition was prepared by dissolving a portion of the resin composition in an acetone-methanol mixed solvent, and the same procedure as in Example 7 was carried out to obtain exactly the same results. Example 10 Formula

1 part of a polymer compound obtained by polymerizing 30 parts of aminoalkyl methacrylate represented by the formula and 70 parts of ethylene and 0.5 part of 4-nitrothioindoxylic acid in a mixed solvent of methyl ethyl ketone/toluene (volume ratio 5/5) dissolved in. The obtained solution was coated with a wire bar on a polypropylene film (60μ thick, trade name Toyobo Pylene Film P1120#60, manufactured by Toyo Kasei Kogyo Co., Ltd.) and dried at 70°C for 5 minutes to form a photosensitive layer with a thickness of 5μ. A photosensitive film was obtained.
This photosensitive film was overlaid with a negative original film and exposed for 6 minutes using a chemical lamp (20W x 10, lamp-photosensitive plate distance 45cm). The exposed film was immersed for 30 seconds in a developer solution in which 0.005 part of bromophenol blue was dissolved in 10 parts of a mixed solvent of water/methanol (volume ratio 4/6) to obtain a deep blue positive image. Halftone resolution is 150 line/inch
That's all. Example 11 50 parts of poly-4-vinylpyridine (manufactured by Koei Chemical Co., Ltd.) and 15 parts of 4-nitrobenzoyl formic acid were dissolved in an acetone-methanol mixed solvent to prepare a uniform solution of a resin composition. Thicken this solution
After coating on a 0.3mm paper surface using a bar coater,
A photosensitive paper coated with a resin composition having a thickness of about 5 μm was obtained by air-drying. The resin-coated surface of the obtained photosensitive paper was exposed for about 3 minutes using the same exposure machine as in Example 10. A printing test was carried out by attaching the exposed photosensitive paper to a fax offset machine (manufactured by Ricoh Co., Ltd.), and as a result, good printed samples were obtained. Example 12 N,N'-bis(aminopropyl)piperazine
26 parts, adipic acid 19 parts and ε-caprolactam
100 parts of polyamide obtained by polycondensing 55 parts of N
- 35 parts of phenylhistidine, 30 parts of ethylene glycol dimethacrylate, 10 parts of benzoyl methyl ether, 0.1 part of hydroquinone methyl ether,
A composition consisting of 15 parts of carbon black and 500 parts of methanol was coated on a biaxially stretched film of polyethylene terephthalate having a thickness of 100 μm and dried to obtain a photosensitive laminate having a thickness of 3 μm. When the active light absorption rate in the wavelength range of 300 to 400 mμ was measured using a spectrophotometer, it was 99.9% or more. The image negative film used in Example 10 was brought into close contact with this photosensitive laminate and exposed for 4 minutes at a distance of 50 cm using a 3 K.W. ultra-high pressure mercury lamp.
After that, we sprayed tap water at a pressure of 2 kg/cm ² from a spray nozzle for about 0.5 minutes, then drained the water and dried it. As a result, we were able to obtain extremely faithful black and white images with dot density ranging from 2% to 90%. Ta. When the positive film containing this black-and-white image was brought into close contact with the unexposed photosensitive laminate described above and the same process was carried out, an inverted black-and-white image in which the halftone dots were faithfully reproduced was obtained. Furthermore, this negative film was brought into close contact with a photosensitive resin plate, Toyobo Printite EF-95, and exposed for 3.5 minutes using the exposure machine used in Example 7. ) at 2.5
After rinsing with water for a minute, a relief plate for relief printing with very good reproducibility was obtained. Using this relief, a printing test was conducted using an automatic letterpress proofing machine (manufactured by Mori Seisakusho), and as a result, a printed sample that reproduced the original image well was obtained. Example 13 The same procedure as in Example 12 was carried out using 40 parts of phenylcarboxymethylcerade in place of the N-phenylhistidine used in Example 12, and the same results as in Example 12 were obtained. . Example 14 0.2 part of tetraisopropyl titanate was added as a catalyst to 258 parts of N,N'-bis(hydroxyethyl)piperazine and 130 parts of dimethyl terephthalate.
100 parts of the resin obtained by polycondensation and 30 parts of N-phenylglycine were completely dissolved and mixed using methanol as a solvent. The obtained solution was applied uniformly to a thickness of 2μ on a 200μ thick aluminum plate that had been anodized.
It was dried with hot air at 50°C for 5 minutes. Next, a negative original film was adhered to this photosensitive plate and exposed for 4 minutes using a high pressure mercury lamp (manufactured by Oak Co., Ltd.: Polymer Printer 3000). After exposure, the photosensitive plate was immersed in water at 20℃PH=7, developed with washer (manufactured by Dainippon Screen), washed with water, drained, and gummed with gum solution GU-2 (manufactured by Fujifilm). and air-dried at room temperature. The resulting printing plate was set in a Ryobi KR480 offset printing machine (manufactured by Ryobi Co., Ltd.) and printed, resulting in a good printed sample that reproduced the original drawing very well. Example 15 Instead of the resin obtained from N,N'-bis(hydroxyethyl)piperazine and dimethyl terephthalate used in Example 14, 100 parts of poly-4-vinylpyridine and 50 parts of N-phenylglycine were used, and methanol was used. Completely mixed and dissolved as a solvent. The obtained solution was processed in exactly the same manner as in Example 14, and a printed sample similar to that in Example 14 could be obtained.

Claims (1)

[Scope of Claims] 1 (1) It has low hydrophilicity or is water-insoluble by itself, but becomes highly hydrophilic or water-soluble due to acid-base interaction in the coexistence with an acidic compound. At least one basic polymer compound having properties such that (2) the following general formula ()
-a, ()-b, ()-c, () and ()
A photosensitive resin composition comprising at least one acidic compound represented by: [Wherein, X is nitrogen, oxygen, sulfur, selenium, R ₁ ,
R ₂ is hydrogen, an alkyl group having 1 to 6 carbon atoms with or without a substituent, a phenyl group, R ₅
is hydrogen, carbon number 1-6 with or without substituents
n is 0 or 1, m is 1 when X is nitrogen, and 0 when X is oxygen, sulfur, or selenium. ] [Wherein, Y is NR ₉ , sulfur, R ₇ and R ₉
are hydrogen, an alkyl group having 1 to 3 carbon atoms, and
R ₈ represents hydrogen, nitro group, cyano group, halogen, or alkoxy group. ] [In the formula, Z is oxygen or sulfur, R ₁₀ is a phenyl group with or without a substituent, and K is 0 or 1
shows. [2] The basic polymer compound is one in which the monomer forming the polymer compound has a group showing basicity, and the basic group shows Pka2 or more as measured by potentiometric titration in an aqueous solvent system. A photosensitive resin composition according to claim 1. 3. A patent claim in which the basic polymer compound is one in which the monomer forming the polymer compound has a basic nitrogen atom, and the nitrogen content in the polymer compound is 0.1 to 25 equivalents/Kg. The photosensitive resin composition according to item 1. 4 Furthermore, at least one selected from aromatic nitro compounds, aromatic ketone compounds, aromatic thioketone compounds, quinone compounds, coumarin compounds, triphenylmethane compounds, triarylpyrazoline compounds, and monoimidazole compounds. Claim 1 containing a kind of photosensitizer
The photosensitive resin composition described in .