JPH0242841B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel photosensitive resin composition, and more particularly to a photosensitive resin composition using a method of photochemically changing the degree of hydrophilicity or water solubility of a polymer compound. 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.
However, the photoreaction rate of the above composition was not sufficient for practical use, so the present inventors conducted research, found a highly sensitive photosensitive resin composition, and proposed a new composition. However, even higher sensitivity than the above-mentioned composition was required, and as a result of further research, the present inventors 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; A basic polymer compound having similar properties, in which the monomer forming the polymer compound has a group exhibiting basicity, and the basic group pka2 or more is determined by potentiometric titration in an aqueous medium. and at least one basic polymer compound having a nitrogen content of 0.1 to 25 equivalents/Kg; (2) acidic in nature;
Chemical changes occur when exposed to light,
Acidic compounds that lose acidity Acidic compounds represented by the following general formula (), 4-nitrothiophenoxyacetic acid, N-phenylalanine, N-phenylglutamine, phenylcarboxymethylselenide, and indoxylic acid. A photosensitive resin composition containing at least one kind and (3) a triarylimidazolyl dimer. [In the formula, R ¹ represents H-, Cl-, NO ₂ -, and R ²

[Formula] indicates -S-, -O-. ] The basic polymer compound used in the present invention means that 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. It can be used in general polymerization reactions such as polycondensation and polyaddition reactions using monomers that have a basic group in the molecule, as shown below, and other monomers if necessary. It includes polymer compounds produced in this manner, or modified polymer compounds obtained by chemically modifying a synthetic polymer compound or a natural polymer compound to impart basicity. 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 are 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 ₁₅ , R ₁₆ , and R ₁₇ are hydrogen residues having 1 to 10 carbon atoms; -15 alkylene group; R ₁₈ and R ₁₉ represent a hydrocarbon residue having 1 to 10 carbon atoms, and R ₁₉ and R ₁₈ may jointly form a ring or a heterocyclic ring. R ₂₀ is a carbon lower alkyl group of numbers 1 to 3 or

[Formula] (where R ₁₈ and R ₁₉ 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. Further, 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
-aminoethyl)-diamines such as 3-methylpiperazine, N-carboxymethylpiperazine,
Examples include ω-amino acids such as N-(4-carboxycyclohexyl)piperazine and N-(2-carboxyethyl)-3-methylpiperazine, or lower alkyl esters thereof. Examples of the monomer represented by the general formula () include N,N'-bis(aminomethyl)piperazine,
Diamines such as N-(aminomethyl)-N'-(2-aminoethyl)piperazine, N,N'-bis(carboxymethyl)piperazine, N,N'-
Bis(carboxymethyl)-2,6-dimethylpiperazine, N-(2-carboxyethyl)-
Dicarboxylic acids such as N'-(carboxymethyl)piperazine or lower alkyl esters thereof, acid halides, and N-(aminomethyl)-N'-(carboxymethyl)piperazine,
Examples include ω-amino acids such as N-(aminomethyl)-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,
Dicarboxylic acids such as N-carboxymethyl-N-(2-carboxyethyl)-methylamine or their lower alkyl esters, acid halides, and N-(aminomethyl)-N-(carboxymethyl)-methylamine, N Examples include ω-amino acids such as -(aminomethyl)-N-(2-carboxyethyl)-isopropylamine, and lower alkyl esters thereof. Examples of the monomer represented by the general formula () include N,N'-dimethyl-N,N'-bis(3-aminopropyl)ethylenediamine, N,N'-dicyclohexyl-N,N'-bis(3-aminopropyl) -aminopropyl) diamines such as hexamethylene diamine, 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)
-N'-(carboxyethyl)hexamethylene diamine and other ω-amino acids or their lower alkyl esters. 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,
There are diamines such as N'-dimethylaminomethyl)-4,8-dioxa-1,11-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. As basic polyesters, there are those that use monomers represented by the following general formulas () to () as polymerization raw materials: [In the formula, R, R′, R″, R, R ₁₅ , R ₁₆ , R ₁₇ ,
R ₁₈ , R ₁₉ and R ₂₀ have the same meanings as above. A', B' are -OH,
-COOH, -COOR′′′′ (here R′′′′ is 1 carbon number
~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-hydroxylopyl-2,5-dimethylpiperazine), N,N'-bis(2-hydroxycycloheptyl)piperazine, N,N'-bis(2-methyl-2-hydroxynonyl)piperazine Examples of the monomer represented by general formula (XI) include N,N'-bis(carboxymethyl)-methylamine, N-carboxymethyl-N-(2-carboxymethyl dicarboxylic acids such as (ethyl)-methylamine or their lower alkyl esters,
These are 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 (XII) 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-hexamethylene diamine. Examples of monomers represented by the general formula () include 2-methyl-2-(N,N-dimethylaminomethyl)-1,3-propanediol, 2-methyl-2-(N,N-diisopropylamino methyl)-1,3-propanediol, 2-methyl-
Examples include glycols such as 2-piperidinomethyl-1,3-propanediol and 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 above general formulas () to (), the raw materials for polymerization of the polyester used in the present invention include aliphatic and/or aromatic dicarboxylic acids or lower alkyl thereof used in the polymerization of ordinary polyesters. Ester, glycol, oxyacid, 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 ₁₅ 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)
Methacrylates such as ethyl methacrylate, 3-(N,N'-diethyl)propyl methacrylate, 3-(N,N'-dimethylamino)propyl methacrylamide, 3-(N,N'-diethylamino)propyl methacrylamide, etc. Examples include 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 mixing amount and mixing ratio of the basic polymer compound and the acidic compound in the composition vary depending on the type of combination of the two, and the properties required for actual use (for example, hydrophilicity before and after irradiation with light, The photoreactive compound is selected based on the difference in water solubility, mechanical properties, reaction rate, etc.), but the total composition contains the photoreactive compound at a ratio of 0.4 to 700g/Kg, and the blending ratio of the two is the acidic compound. It is preferable that the equivalent ratio of the acidic group and the basic nitrogen contained in the basic polymer compound be 0.02 to 1. In the present invention, the triarylimidazolyl dimer is represented by the following general formula (), and the dimer generates free radicals when irradiated with light, causing or promoting a chemical change that reduces the acidity of the acidic compound. This significantly improves sensitivity. In the formula, Ar, Ar′, and Ar″ each represent an aryl group with or without a substituent group. In the present invention, when Ar is a phenyl group, a group having a substituent at the ortho position of the phenyl group , and when Ar is a 1-naphthyl group, 1-
Those having a substituent at the 2-position of the naphthyl group are preferred. Specifically, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer,
2-(o-chlorophenyl)-4,5-(m-dichlorophenyl)imidazolyl dimer, 2-(o
-Chlorphenyl)-4,5-(m-dianisyl)imidazolyl dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolyl dimer, 2-(o-methoxyphenyl)-4 , 5-diphenylimidazolyl dimer, 2-(o-nitrophenyl)-4,5-diphenylimidazolyl dimer, 2-(p-nitrophenyl)-4,5-diphenylimidazolyl dimer, 2- (o-promophenyl)-4,6-diphenylimidazolyl dimer, 2-(1-naphthyl)-4,5-diphenylimidazolyl dimer, 2-(2-chloro-1-
Examples include (naphthyl)-4,5-diphenylimidazolyl dimer. Note that the above dimer is a dimer of the same lofin, but of course dimers of different lofins are also included, for example, 2
-phenyl, 2'-(o-chlorophenyl, 4,
4′,5,5′-tetraphenyl)biimidazole,
2-(o-chlorophenyl)-2'-phenyl,
Examples include 4,5-(dimanisyl)-4,5'-diphenylbiimidazole. The triarylimidazolyl dimer is contained in an amount of 1% to 50% by weight, preferably 1% to 20% by weight, based on the total composition, and the equivalent ratio of the dimer to the acidic compound is 0.1 to 2.0. It is preferable to do so. In the composition of the present invention, sensitivity can be increased by further adding a photosensitizer. Examples of the photosensitizer used in the present invention include 4,4'-bisdimethylaminobenzophenone,
Aromatic ketone compounds such as thioxanthone, fluorenone, trinitrofluorenone, 4,4'-
Aromatic thioketone compounds such as bisdimethylaminothiobenzophenone, benzoquinone, dichlorobenzoquinone, tetrachlorobenzoquinone, dichlornaphthoquinone, phenanthrenequinone, dichloroanthraquinone, dinitroanthraquinone,
Quinone compounds such as alizarin and benzanthraquinone, aromatic nitro compounds such as dinitrofluorene, tetranitrofluorene, trinitrofluorene, nitroacenaphthene, 2,4,6-trinitroaniline, and triarylpyra such as triphenylpyrazoline. Zolin compounds, monoimidazole compounds such as tetraphenylimidazole and triphenylimidazole, xanthene compounds such as fluorescein, eosin Y, rose bengal, erythrosin B, and phloxine, acridine compounds such as acriflavin and riboflavin, 7-N - Coumarin compounds such as dimethylaminocoumarin, triphenylmethane compounds such as thymol blue, bromothymol blue, and bromucresol green, among others aromatic ketone compounds, quinone compounds, aromatic nitro compounds, and triaryl compounds. Pyrazoline compounds,
Coumarin compounds are preferred. The amount of the photosensitizer is 0.1 to 10% by weight, preferably 0.1 to 10% by weight based on the total composition.
It may be added in an amount of 0.1 to 5.0% by weight. If necessary, the composition of the present invention may be used in combination with an acidic compound that does not lose its acidity even when irradiated with light even in the coexistence of a photoactive compound, so as to eliminate the difference in hydrophilicity or water solubility before and after irradiation with light. It is also possible to control. 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 glycidimethacrylate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-propanediol acrylate, 1, Monomers having two or more unsaturated double bonds such as 3-propanediol methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triacryloyloxyethyl phosphate, methylenebisacryamide, methylenebismethacryamide, etc. be. In preparing the composition of the present invention, a basic polymer compound, an acidic compound, a triarylimidazolyl dimer and, if necessary, a photosensitizer are dissolved in an appropriate solvent and mixed uniformly. A method is employed in which an acid-base pair is formed between a neutral polymer compound and an acidic compound. Suitable solvents include methanol,
Lower alcohols such as ethanol and isopropanol, acetone, ketones such as methyl ethyl ketone, esters such as methyl cellosolve and ethyl cellosolve, aromatic compounds such as toluene and xylene, or mixtures of two or more thereof can be used. However, if the basic polymer compound used is liquid at room temperature or its melting point is
When the softening point and pour point are relatively low, 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 interposed therebetween. Any material such as steel, aluminum, plastic film, glass, etc. can be used as the support. 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 may be carried out by scanning a desired image or pattern image as a locus over the image of the composition of the present invention with a light beam from such a light source. 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 object with light is utilized without changing the form of the layered object, and etching or washout operations with water. 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,
Examples of the latter use include various negative resists and offset printing plates, and reliefs such as letterpress printing resin plates, name plates, molds for molds, and resin molds for embossing. Can be mentioned. 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 composition of the present invention having the above configuration is characterized by the selection of each of the three main components (basic polymer compound, acidic compound, and triarylimidazolyl dimer) and mutual interaction. By combining the quantitative 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. Furthermore, since the photoreaction of the composition of the present invention does not proceed through a chain reaction, the resolving power is extremely high.
Unlike dimensional reactions, there is no volume contraction after light irradiation, that is, no image formation, 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 guarantees a particularly favorable working environment and operability in terms of safety. Furthermore, the composition of the present invention has an extremely fast photoreaction rate, so it can be put to practical use. 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. Example 1 2-methyl-2-(N,N'-dimethylamino)
Polyester 1 obtained by direct polymerization from methyl-1,3-propanediol and terephthalic acid
1 part, 0.4 part of N-phenylglycine, and 0.15 part of 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer were dissolved in 8 parts of methyl ethyl ketone. The obtained solution was applied onto art paper whose surface had been previously coated with a conductive treatment agent (trademark product: Dow ECR34, manufactured by Dow Chemical Company) and dried, and dried in a hot air dryer at 70°C for 5 minutes to a thickness of 6 μm. A photosensitive paper having a top layer of . A negative original film was layered on this photosensitive paper and exposed for 2.5 minutes using a chemical lamp (20W x 10, distance between lamp and photosensitive paper 45mm). Transfer the exposed photosensitive paper to an electronic copying machine (trade name: Copistar 211).
(manufactured by Sanda Kogyo Co., Ltd.), a positive image was obtained in which toner adhered only to the exposed areas. The halftone dot resolution was 150 lines/inch. Example 2 The exposed photosensitive paper obtained in Example 1 was set in an electrostatic transfer device (trademark product: Xerox 1385, manufactured by Rank Xerox), and electrostatic transfer was performed on art paper by a cascade method. However, a clear toner image was formed on the art paper. When the transfer was repeated by cleaning the photosensitive paper after transfer with absorbent cotton and setting it on the electrostatic transfer device again, a large number of identical copies were obtained, and even after 30 trials, the images remained exactly the same. Ta. Incidentally, the charging voltage of the photosensitive paper and its change over time were measured using a static honest meter (trade name: manufactured by Anato Shokai Co., Ltd.) for unexposed areas and exposed areas at -15 KV discharge. The charging voltage at the time of exposure and one month after exposure was 300 V in both the unexposed areas and 15 V in both the exposed areas. Such performance shows that the composition of the present invention is suitable for a negative-positive type electrostatic printing original plate. Example 3 The composition solution of Example 1 was uniformly coated on a 200 μm thick anodized aluminum plate to a thickness of 2 μm, and dried with hot air at 50° C. for 5 minutes. A negative tape original film was closely attached to the photosensitive plate, and exposed for 2.5 minutes using a high-pressure mercury lamp (Polymer Printer 3000, manufactured by Offu Co., Ltd.). After exposure, the photosensitive plate was immersed in water at 20°C and pH=7, 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 (GU manufactured by Futo Film Co., Ltd.). After air drying at room temperature, print using an offset printing machine (manufactured by Ryobi Co., Ltd.).
As a result of printing tests using the KR480 model, good print samples were obtained. Comparative Example 1 Photosensitive paper B was obtained in the same manner as in Example 1 except that 2-(o-chlorophenyl)-4.5-diphenylimidazolyl dimer was not blended. An attempt was made to obtain a positive image in which toner adhered only to the exposed areas using the obtained photosensitive paper B in the same manner as in Example 1, but in order to obtain the same dot resolution as in Example 1, the photosensitive paper B required an exposure time of 5 minutes. Example 4 Formula; 1 part of a polymer compound obtained by polymerizing 50 parts of aminoalkyl methacrylate and 50 parts of methyl methacrylate, 0.35 part of phenylglycine,
0.2 part of 2-(o-chlorophenyl-4,5-(m-dianisyl)imidazolyl dimer, 0.05 part of triphenylpyrazoline, and carbon black)
A composition consisting of 0.15 parts of tetrahydrofuran and 8 parts of tetrahydrofuran was applied onto a biaxially stretched polyethylene terephthalate film 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 Examples 4 and 5 was brought into close contact with this photosensitive laminate, and a 3KW ultra-high pressure mercury lamp was used.
Exposure was carried out for 2 minutes at a distance of 50 cm. After that, spray approximately 0.5 liters of tap water at a pressure of 3 kg/cm ² from the spray nozzle.
After spraying for a minute and drying immediately, extremely faithful black and white images with dot densities ranging from 2% to 90% were obtained. 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 negative 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 RF-95, and exposed for 4.5 minutes using the exposure machine used in Example 1, and then washed with water for 2.5 minutes using the washing machine for Toyobo Printite. A very good relief plate for letterpress printing was obtained. Example 5 1 part and 2 parts of a polymer compound obtained by polymerizing 30 parts of diethylaminoethyl methacrylate and 70 parts of ethylene
-0.1 part of (o-chlorophenyl)-4,5-(m-dianisyl)imidazole dimer and 0.3 part of 3-chlorophenylglycine were mixed with methyl ethyl ketone/
It was dissolved in a mixed solvent of toluene (volume ratio 5.5/4.5). The obtained solution was coated with polypropylene film (thickness 60μ, trade name: Toyobo Pylene Film P1120).
#60. (manufactured by Toyo Kasei Kogyo Co., Ltd.) with a wire bar and dried at 70° C. for 5 minutes to obtain a photosensitive film having a photosensitive layer with a thickness of 5 μm. A negative original film was layered on this photosensitive film and exposed for 1.5 minutes using a chemical lamp (20W x 10; distance between lamp and photosensitive paper 45mm). 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 form a deep blue positive image. Halftone resolution is 150 line/inch
That's all. Example 6 Polyamide 100 obtained by polymerizing 40 parts of N-(β-aminoethyl)piperazine, 50 parts of adipic acid and 38 parts of ε-caprolactam, 50 parts of 4-nitrophenylglycine, 2-(2'-chloro After dissolving 20 parts of -1'-naphthyl)-4,5-(m-dianisyl)imidazole dimer and 3 parts of 7-N-dimethylaminocoumarin in methanol, the solution was cast and pasted on a 28 mm iron plate. Combined. An image negative produced by 150 line/inch mesh resolution was adhered to the photosensitive original plate thus obtained, and exposed for 5 minutes using a chemical lamp with an illuminance of 200 W/cm ² . Thereafter, the material was brushed for 1 minute while immersed in tap water with a pH of 7.5, and then dried with warm air at 60° C. for 10 minutes. The obtained relief plate showed faithful correspondence to the image negative, and the shoulder angle of the relief cross section was about 70 degrees. Using this relief plate, we conducted a printing test using an automatic letterpress proofing machine (manufactured by Mori Seisakusho), and found that
A printed sample that reproduced the original image well was obtained. Furthermore, the surface of the relief plate was covered with cellophane tape, leaving a part of the image, and then sprayed with water at pH 4.0 for 0.5 minutes to wash it out. After peeling off the cellophane tape and drying it, a printing test similar to that described above was carried out, and a print was obtained in which the mesh image in the uncoated area was much brighter than in the other areas. Example 7 50 parts of poly-4-vinylpyridine (manufactured by Koei Chemical Co., Ltd.), 7 parts of 4-nitrothiophenoxyacetic acid,
A homogeneous resin composition solution was prepared by dissolving 10 parts of 2-(o-nitrophenyl)-4,5-diphenylimidazole dimer and 3 parts of fluorescein in an acetone-methanol mixed solvent. This solution was applied to a paper surface with a thickness of 0.3 mm using a bar coater, and then air-dried to obtain a photosensitive paper coated with the resin composition with a thickness of about 5 μm. The negative film used in Example 4 was brought into close contact with the resin-coated surface of the resulting photosensitive paper, and exposed for about 4 minutes using the same exposure machine as in Example 4. 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. Examples 8 to 17 In Example 1, a predetermined amount of the acidic compound shown in Table 1 and a photosensitizer were added in place of N-phenylglycine, or the thickness was increased in the same manner as in Example 1 without adding a photosensitizer. A photosensitive paper having a top layer with a thickness of 3 μm was obtained.
Each of the obtained photosensitive papers was overlaid with a negative tape original film, exposed for each time period in the same manner as in Example 1, and passed through an electronic copying machine to obtain a positive image.
The resolution of each dot is also listed in Table 1.

【table】

[Table] Example 18 1 part of a polymer compound obtained by polymerizing 56 parts of N-dimethylaminoethyl methacrylate and 44 parts of methyl methacrylate, 2-(O-chlorophenyl)-4,5-(m-dianisyl)imidazole Dimer 0.24 parts, 4-nitrophenylglycine 0.4
and 0.05 part of triphenylpyrazoline, plus 0.15 part of carbon black and tetrahydron.
A composition consisting of 10 parts is applied onto a biaxially stretched film of polyethylene terephthalate having a thickness of 100μ,
A photosensitive laminate having a thickness of 3 μm was obtained by drying. 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 Examples 4 and 5 was brought into close contact with this photosensitive laminate, and exposed for 2 minutes at a distance of 50 cm using a 3KW ultra-high pressure mercury lamp.Then, water pressure of 3Kg/cm ² was applied from a spray nozzle. As a result of spraying tap water for about 0.5 minutes and drying immediately, extremely faithful black and white images with halftone dot density ranging from 2% to 90% were obtained. 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 negative image in which the halftone dots were faithfully reproduced was obtained. Furthermore, this negative film is printed on a photosensitive resin plate and a Toyobo printer printer.
The exposure machine used in Example 1 was used in close contact with RF-95.
A very good relief plate for letterpress printing was obtained by exposing for 4.5 minutes and washing with water for 2.5 minutes using a washing machine for Toyobo Printite. Example 19 The same procedure as in Example 18 was carried out using 0.3 part of Sn-butylthioacetic acid instead of the organic acid compound 4-nitrophenylglycine, and the same results were 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. A basic polymer compound having properties such that the monomer forming the polymer compound has a group showing basicity, and the basic group is determined by potentiometric titration in an aqueous medium. pka2 or more, and the nitrogen content in the polymer compound is
At least one type of basic polymer compound having an amount of 0.1 to 25 equivalents/Kg; (2) an acidic compound that is acidic in nature and loses its acidity through an optical change when exposed to light; An acidic compound represented by the formula (), at least one selected from 4-nitrothiophenoxyacetic acid, N-phenylalanine, N-phenylglutamine, phenylcarboxymethylselenide and indoxylic acid, and (3 ) A photosensitive resin composition containing a triarylimidazolyl dimer. [In the formula, R ¹ represents H-, Cl-, NO ₂ --, and R ² represents [Formula] -S-, -O-. ]