JPS6161094B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to the production and lamination of printing plates such as plano relief plates, gravure plates, and scouring printing plates using flat plates such as so-called PS plates, zinc plates, and multilayer metal plates provided on a support with a hydrophilic surface.・Production of flexible printed wiring boards, production of other chemically milled metal products, etc., production of exposure originals in which a highly colored photosensitive layer is placed on a transparent or translucent support to form a high contrast image,
The present invention also relates to a so-called negative-type photocurable photosensitive material that can be developed with alkali and can be used for a wide range of purposes, such as creating patterns for decoration and marking. The inventors have already applied for a photosensitive material comprising two types of non-functional binary copolymers, a crosslinking agent and a photoactive agent, and a method for using the same (filed on December 30, 1972), but this invention The object of the present invention is to provide a photosensitive material having one of its characteristics of exhibiting higher sensitivity, and the present invention will be described in detail below. The photosensitive material is a binary copolymer (hereinafter referred to as a copolymer for convenience) composed of two types of monomers represented by the general formula () (CH ₂ = CHAr) _n1 (HOOCCH = CHCOOR ₁ ) _n2 ......() [However, in formula (), Ar represents a phenyl group or a substituted phenyl group, R ₁ represents a lower alkyl group, and the numbers m ₁ and m ₂ represent the presence of the monomer in the copolymer, respectively. Indicates the ratio m ₁ ≧ m ₂ . ] and a ternary copolymer composed of three types of monomers represented by the general formula () (hereinafter referred to as a copolymer for convenience) [CH ₂ =C(R ₂ )COOR ₃ ] _o1・[CH ₂ = C(R′ ₂ )COOR ₄ ] _o2・[CH ₂ =C(R″ ₂ )COOH] _o3 ………() [However, R ₂ , R′ ₂ , R″ ₂ in formula () Hydrogen atom or methyl group, R ₃ is methyl group or ethyl group, R ₄
represents an isobutyl group or a tertbutyl group, and the numbers n ₁ , n ₂ , and n ₃ represent the abundance ratio of each monomer in the copolymer, and n _1kiO , n _2kiO , (n ₁
+ _n2 ) _/n3=0.5~20 . ] It is characterized by containing two types of polymeric compounds at the same time, including a crosslinking agent and a photoactivator, and various other subcomponents depending on the purpose of use, such as a thermal polymerization inhibitor, a coloring agent, and a thixotropic agent. It consists of a mixture of agents, surfactants, etc. First, each component constituting the photosensitive material will be explained. As mentioned above, a photoactivator, a crosslinking agent having a functional group, a binder for various subsidiary components, and a polymer compound that has the function of being crosslinked and photocured by the crosslinking agent when irradiated with actinic light. Copolymers and copolymers are used simultaneously. The copolymer and the copolymer have free carboxyl groups because the unexposed areas of the exposed photosensitive layer provided on the surface of the substrate can be removed by a weakly alkaline developer. Specifically, the copolymer is styrene, α-
Styrenes such as methylstyrene, vinyltoluene, O- or p-chlorostyrene, O- or p-methoxystyrene, monomethyl maleate, monoethyl maleate, mono-n-maleate
1 each from propyl, iso-propyl maleate, mono-n-butyl maleate, mono-iso-butyl maleate, mono-tert-butyl maleate, etc.
It is a copolymerized polymer compound of selected styrene or styrene derivatives and monoalkyl maleate. However, for the purpose of this invention, styrene and monomethyl maleate, -N-
Preference is given to combinations of propyl, iso-propyl maleate, mono-N-butyl maleate, iso-butyl maleate or mono-tert-butyl maleate. The abundance ratio in the copolymer of styrene or its derivatives and monoalkyl maleate is
m ₁ /m ₂ =5 to 1 is desirable, and the repeating unit of the copolymer, i.e., -CH(Ar)-CH-CH
The number of (COOH)-CH( _COOR1 )- used is relatively low, with a degree of polymerization of about 6 to 15. However, there are no restrictions on the degree of polymerization. The copolymer is easily synthesized by methods known in the art. For example, styrene and maleic anhydride are subjected to conventional radical polymerization to form poly(styrene-CO-maleic anhydride), which is then dissolved in a lower alcohol solvent. Poly(styrene-CO-monoalkyl maleate) can be obtained by dispersing it and heating it until it dissolves without removing the water produced.
The alkyl group here is the alkyl residue of the lower alcohol used. Specifically, the copolymer is one selected from methyl methacrylate (or acrylate), ethyl methacrylate (or acrylate), isobutyl methacrylate (or acrylate), and methacrylate (or acrylic acid). It is obtained by copolymerizing one type selected from tert-butyl acid and three types of monomers such as methacrylic acid (or acrylic acid), and has a relationship of (n ₁ + n ₂ )/n ₃ = 0.5 to 20. Something is desirable. As mentioned above, since the copolymer can be developed with a weak alkali, methacrylic acid or acrylic acid is copolymerized to retain free carboxyl groups. When the amount of free carboxyl groups, that is, n ₃ , exceeds a certain limit, the photocured portion also tends to swell with the alkaline developer, so there is an appropriate range for n ₃ . Copolymers can also be synthesized by applying conventional methods, and some examples will be given below. Reference Example 1 In a reactor with a stirrer equipped with a nitrogen inlet, add commercially available kerosene 1 treated with calcium chloride for drying, purge with nitrogen at 70°C, and add 255.6 g of tert-butyl methacrylate, 60 g of methyl methacrylate, and methacrylate under a nitrogen atmosphere. Acid 51.6g (Preparation molar ratio 6:
2:2), 3 g of benzoyl peroxide, and 1.5 ml of n-dodecylmercabutane was added dropwise over 15 minutes, and after the addition was completed, the temperature was maintained at 80°C. Residue
Add 2/3 of the above mixture dropwise over 2 hours and do the same.
The mixture was kept at 80°C and reacted for 5 hours. During this time, the produced polymer begins to precipitate, so do not use kerosene.
200ml was added in 4 portions. After cooling, heat drying under reduced pressure to obtain poly(tert-butyl methacrylate).
344 g of CO-methyl methacrylate-CO-methacrylic acid was obtained. Yield 94%, acid value 95.9, [η]
²⁵ °C _MC = 0.208 (MC stands for methyl cellosolve), ir
.
Characteristic absorption (KBr tablet method) 3400cm ^-1 (ν OH,
S), 2960cm ^-1 (ν asym, CH, m), 1720cm ^-1
(ν C=O, S), 1460cm ^-1 (δ asym, CH,
w ~ m), 1370cm ^-1 , 1390cm ^-1 doublet (δ
sym, CH, m), 1260cm ^-1 (-C(CH) skeleton,
m), 1140cm ^-1 , 1270cm ^-1 (ν -C-O-,
S, m) However, S, m, and w in parentheses indicate strong, moderate, and weak absorption peaks, respectively, and the attribution is for separately synthesized poly(tert-butyl methacrylate-CO-methacrylic acid) and poly(methyl methacrylate-CO).
- methacrylic acid). Reference Example 2 Using the same method and reaction conditions as Reference Example 1,
Poly(tert-butyl methacrylate) was reacted with a composition of 99.4 g of tert-butyl methacrylate, 20.0 g of methyl methacrylate, 5.6 g of methacrylic acid (charged molar ratio 7:2:1), 1 g of benzoyl peroxide, and 0.4 ml of n-todecylmercabutane. -CO-methacrylic acid) 102g was obtained. Yield 80%, acid value 46.9, [η]
²⁵ °C _MC = 0.358. The characteristic absorption of ir was the same as that of Reference Example 1. Reference Example 3 Using the same method and reaction conditions as in Reference Example 1, replacing the dispersion medium with ISOPAR-E (manufactured by Etsuso, USA, alkane-based solvent), 78.5 g of isobutyl methacrylate, 15 g of methyl methacrylate, 5.6 g of methacrylic acid ( (Charging molar ratio 5.5:1.5:3), 1 g of benzoyl peroxide, and 1 ml of n-dodecylmercabutane were reacted in 350 ml of dispersion medium to obtain 107 g of poly(isobutyl methacrylate-CO-methyl methacrylate-CO-methacrylic acid). Yield 90%, acid value 169.6,
[η] ²⁵ °C _MC = 0.232. IR characteristic absorption 3400cm ^-1 (ν

OH.m) 2950cm ^-1 (ν asym CH, m), 1730cm
^-1 (ν C=O, S), 1470cm ^-1 (asym CH
m), 1390cm ^-1 , 1370cm ^-1 doublet (δ sym CH
m~w), 1270cm ^-1 (ν -C-O-, m), 1170
(

[Formula] Skeleton, S). Reference example 4 Using the same reaction device as in reference example 1, the stirrer was set to 250
Operating at ~300 rpm, under nitrogen atmosphere, 21.3 g of butyl methacrylate, 5 g of methyl methacrylate, 4.3 g of methacrylic acid (molar ratio of 6:2:
2) Add 0.3 g of benzoyl peroxide, 0.2 ml of n-dodecylmercabutane, and 0.8 g of polyethylene oxide (POLYOX-WSR-N-80 manufactured by Union Carbide, USA, molecular weight 2 x 10 ⁵ ), and heat at 75 to 80°C.
Pearl polymerization was carried out for 3 hours and washed separately with water to form white beads of poly(tert-butyl methacrylate-CO-methyl methacrylate-CO-methacrylic acid) 25.3
I got g. Yield 83%, acid value 82.2, [η] ²⁵ °C _DMF =
0.176
(DMF is an abbreviation for N-N-dimethylformamide) i.
r. Characteristic absorption was the same as Reference Example 1. A photosensitive layer obtained using a photosensitive material prepared by adding a crosslinking agent and a photoactive agent described below to a copolymer or a copolymer alone does not exhibit sufficiently satisfactory performance. The speed was considerably low, the layer formation properties were not good, and the photocured portions became fine pieces and easily peeled off. Photosensitive layers using only copolymers had defects such as tackiness due to insufficient inclusion of the liquid crosslinking agent added. It has been discovered that by simultaneously using a copolymer, it is possible to prepare a photosensitive system with various characteristics without causing any practical problems. It is essential that the copolymer has an isobutyl group or a tertbutyl group. The copolymer has the advantage that the photosensitivity is particularly high compared to when this type of group is replaced by a methyl, ethyl, isopropyl, or n-butyl group. The basis for this is, for example, methyl groups, isopropyl groups, and
Since the delocalization energies of the tert-butyl group correspond to 0, 4, and 12 kcal/mol, respectively,
It is assumed that in this order, CH ₄ →・CH ₃ +・
The energy required to dissociate into H and (CH ₃ ) ₃ CH→・C(CH ₃ ) ₃ +・H (bond dissociation energy) is also 102 and 90 Kcal/mol, respectively (for example, C.
Walling, Free Radicals in Solutiou, published by J. Wiley.
1967, p-50). Note that the above description is intended to be illustrative and does not limit the content of the present invention. From this point of view, it is easier to synthesize by using a binary copolymer of isobutyl methacrylate (or acrylate) or tert-butyl methacrylate (or acrylate) and methacrylic acid (or acrylic acid) instead of a copolymer. It is considered to be more advantageous in terms of photosensitivity and speed, and this has been experimentally proven. However, when the binary copolymer is used alone or in combination with a copolymer, there is a problem in the leveling property during the formation of the photosensitive layer. This drawback can be overcome by using a copolymer, which is a terpolymer, and also has a high photosensitive speed.
In the range of n ₁ /n ₂ =5 to 0.2, no substantial difference from the above-mentioned binary copolymer was observed. The weight ratio of the copolymer to copolymer in the photosensitive material is usually set in the range of /=5 to 0.2,
Generally, the smaller the value of /, the higher the photosensitive speed tends to be. Additionally, the larger the value of /, the stronger the adhesion to the substrate surface. Therefore, the value of / must be selected depending on the intended use of the photosensitive material. On the other hand, when comparing a photosensitive system containing a copolymer with a photosensitive system containing a copolymer and a binary copolymer of methyl methacrylate (or acrylate) or ethyl methacrylate (or acrylate), the former system is It has the advantage that the photosensitive speed is about 2 to 10 times higher than that of the system, and the strength of the photocured layer is also high. The difference between the two became more pronounced as the thickness of the photosensitive layer became thinner. This fact is illustrated in the examples below. As the crosslinking agent contained in the photosensitive material, a compound having a boiling point of 150°C or higher at room temperature and having two or more ethylenically unsaturated groups is used, and a compound having two or more azide groups is also used. Is possible. Specific examples of compounds having two or more ethylenically unsaturated groups include furfuryl acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, hexamethylene glycol diacrylate, and neopentyl glycol diacrylate. , trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, resorcinol diacrylate, p-p′-dihydroxydiphenyl diacrylate, bisphenol A digcyldyl diacrylate, and the above methacrylate isoconstructs, i.e. furfuryl methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexamethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate. , resordinol dimethacrylate, p.
p′-dihydroxydiphenyl dimethacrylate,
Bisphenol A diglycidyl dimethacrylate, etc., or diaryl phthalate, diarylacrylamide, methylene bisacrylamide,
5,5-diarylbarbituric acid and the like are typical. Compounds with two or more azide groups include p.p'-diphenylbis(azido)methane, p.p'-bis(azido)benzophenone,
Examples include p.p'-bis(azido)azobenzene, or a compound obtained by converting the diazo group of a cocondensate of p-diazodiphenylamine and formaldehyde into an azide group. As seen in the example above, if the crosslinking agent has good compatibility with the copolymer, there will be no problem when developing with a weakly alkaline aqueous developer; It does not need to be soluble in liquid. The crosslinking agent added to the light-sensitive material is selected from the compounds listed above or their green-like compounds, depending on the photosensitivity,
The crosslinking agent is selected in consideration of the corrosion resistance of the photocrosslinked layer or the compatibility with the above-mentioned copolymer, and two or more types of crosslinking agents may be added at the same time.
The amount of crosslinking agent in the photosensitive material is preferably in the range of 10% to 100% of the weight of the copolymer or mixture, but it can be set outside this range depending on the purpose of use. As photoactivators, ketones and their various derivatives, or quinoid compounds such as benzophenone, benzyl, p.p'-bis(dimethylamino) are used.
benzophenone, p・p′-bis(diethylamino)benzophenone, benzoin ethyl ether, benzoin isopropyl ether, anthraquinone, acenaphthenequinone, β-tertbutylanthraquinone, phenanthrenequinone or isoconstructs of ketones such as p・p′-bis (dimethylamino)thiobenzophenones, some heterocyclic compounds such as primulin, carbazole, N-methyl-3-nitrocarbazole, xanthone, thioxanthone, or polyhaloalkanes and their derivatives such as carbon tetrabromide, ω, ω, A variety of known photoactive agents are utilized, such as ω-tribromomethylphenyl sulfone. The amount of the photocrosslinking agent added is selected in the range of 0.01 to 20%, preferably 0.1 to 10%, based on the total weight of the copolymer and the crosslinking agent. In addition, when using a compound containing an ethylenically unsaturated group as a component contained in a light-sensitive material, it is desirable to use an ordinary thermal polymerization inhibitor to suppress dark reactions during storage.For this purpose, hydroquinone , p-methoxyphenol, pyrogallol,
2,6-di-tert-butyl-p-cresol, Kyuferon, etc. are used. The amount of thermal polymerization inhibitor added depends on the total weight of copolymer and crosslinking agent.
It is usually determined within the range of 0.001 to 1%. It is also known as a coloring agent to facilitate the identification of photosensitive layers and photocrosslinked images when photosensitive materials are used for printing plates, printed wiring boards, chemical milling, and other fine processing of planar substrates. It can be colored by adding dyes or finely divided pigment particles. In addition, a surfactant is added during photosensitive layer formation to improve leveling properties and wettability to the substrate surface. Specific examples of colorants and surfactants are described in the Examples. When producing high-contrast images or producing patterns for decoration and marking using photosensitive materials, it is particularly preferable to use dyes at high concentrations, unlike the purpose of identifying photosensitive layers and photocrosslinked images. requires the addition of pigment. In particular, it is desirable to use a black pigment such as carbon black or iron black to create a high contrast image, and the amount of pigment added is 10% of the total weight of the copolymer and crosslinker
~300%, and this is also the case for design pattern making, using various toned dyes with yellow, orange, red, blue, green, or black and white as the main tones, preferably with the same pigment content. added. When a photosensitive material is used for this type of image formation, it goes without saying that a colorant is one of the essential components, and is selected from various commercially available dyes and pigments. Incidentally, for purposes of simply identifying photosensitive layers and photocrosslinked images, the amount of colorant added is usually within the range of 0.05 to 5% of the total weight of the copolymer and crosslinking agent. Describe how to use photosensitive materials. Photosensitive materials can be thermally melted and formed into injection sheet or film shapes.
Although it can be used when a thickness of 100 μm or more is required, the photosensitive layer is usually formed by dissolving the photosensitive material in an organic solvent, casting it onto the surface of the substrate, and evaporating the solvent. Organic solvents used for this purpose include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, cellosolves (ethylene glycol monoalkyl ether) such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, and cellosolves such as methyl cellosolve acetate and ethyl cellosolve acetate. Lower fatty acid esters such as the above, other alcohols such as methyl alcohol, tetrahydrofuran and dioxane, cyclic ethers, polar solvents such as N-methylpyrrolidone and DMF are used alone. Also, alcohols such as ethyl alcohol, isopropyl alcohol, benzene, xylene, monochlorobenzene, ethyl acetate, butyl acetate, isoamyl acetate, or dichloromethane, benzenoid solvents, esters,
Haloalkanes may be mixed with the above-mentioned solvents that can be used alone and used as a solvent for photosensitive materials. The viscosity of the solvent solution of the photosensitive material, that is, the photosensitive liquid, varies depending on the purpose of use and the coating method used to form the photosensitive layer, but is usually adjusted to about 10 cps to 500 cps. The photosensitive liquid can be applied to the surface of the substrate using a rotary coating machine such as a roll coater, spinner (or whaller), etc. and dried to form a photosensitive layer, as well as spray coating, dip coating, wire bar coating, gravure roll coating, etc. It can also be applied by. The photosensitive liquid is applied using a method known in the art. The photosensitive layer can be exposed directly through the original using a film that transmits active light, without the need for a protective film or a protective layer that is normally provided on top of the photosensitive layer. The active light source that photo-crosslinks the exposed portion of the photosensitive layer and makes it insolubilized in a weakly alkaline developer includes low-pressure, medium-pressure, high-pressure,
Alternatively, ultra-high pressure mercury lamps, metal halide-containing mercury lamps, carbon arc lamps, xenon lamps, etc. are advantageously used. After exposure, the unexposed areas can be easily removed by immersing the photosensitive layer on the substrate in an aqueous solution of a few percent of an inorganic weak base such as sodium carbonate or sodium silicate, or an organic base such as ammonia or ethanolamine, and the original image can be removed. A negative image of is formed on the substrate surface. Depending on the purpose of use, it may be necessary to peel off the photocrosslinked portion after completing processes such as corrosion and plating. In that case, peeling can be easily carried out by immersing it in an approximately 5% caustic alkali aqueous solution. The photosensitive materials will be described in more detail below with reference to Examples. Note that parts in the examples represent parts by weight.
In addition, in the following description, copolymers and other comparative examples 2
For the original copolymer, the molar ratio of the constituent monomers is the abundance ratio in the copolymer, and for the copolymer, the molar ratio of the constituent monomers is the monomer charging ratio at the time of copolymer synthesis. are shown respectively. Example 1 (Copolymer) Poly(styrene-CO-monoisopropyl maleate) (molar ratio 1:1) 50 parts (Copolymer) Poly(tert-butyl methacrylate-) of Reference Example 1
CO-methyl methacrylate-CO-methacrylic acid) (molar ratio 6:2:2) 50 parts (crosslinking agent) Triethylene glycol diacrylate 40 parts ethylene glycol diacrylate 30 parts (photoactivator) Benzoin ethyl ether 8 parts p. p′-bis(dimethylamino)benzophenone
2 parts (thermal polymerization inhibitor) p-methoxyphenol 0.01 part (colorant) CI Solvent Blue 73 1 part (surfactant) Polyoxyethylene sorbitan monolaurate
0.5 parts Dissolve the above in 900 parts of ethyl cellosolve
A photosensitive solution of 45 cps (25°C) was obtained. A dry film thickness of 3 is applied to an aluminum plate whose surface has been surface-treated by ball polishing and anodizing using a roll coater.
A lithographic printing plate was prepared by providing a photosensitive layer of μ. A negative printing original is vacuum-adhered to the photosensitive layer of the above printing plate, and an ultra-high pressure mercury lamp (3kW) is applied at a distance of 1m.
It was irradiated for 40 seconds (light intensity 4.7 mW/cm ² ). The exposed printing plate was immersed in a 3% sodium silicate aqueous solution at 20° C. for 1 minute, washed with water, rinsed with 3% phosphoric acid, washed again with water, coated with gum arabic solution and dried to obtain a positive printing plate. The printing plates were run on an offset printing machine and over 200,000 copies of well-printed prints were obtained. Further, after storing the above printing plate for 18 months, the sensitivity, developability, resolution, ink receptivity of the plate surface, ink transferability, etc. were examined in detail, but no changes were observed. Examples 2 to 7 The total weight of copolymers was 100 parts, the ratios of copolymers, and were changed as shown below (Table 1), and all other components had the same composition as in Example 1. The test results shown in Table 2 were obtained for lithographic printing plates and printing plates prepared by the same method. In addition, for the comparative example listed for reference, the total weight of the copolymer and binary polymer was 100 parts, and all other ingredients, printing plates, and printing plate preparation methods were the same as in Example 1 for comparison. And so.

【table】

【table】

[Table] The evaluations in Table 2 correspond to A-excellent, B-good, and C-fair to poor. Coatability - Judgment is made based on whether a uniform film surface is formed using a roll coater and a rotary coater (rigid Whaler); evaluation C corresponds to "Fail". Sensitivity - √2 step tablet (Kodak Step
Tablet No. 2) Judging by the time required to bake until 6-step solidity and the strength of the cured film. Evaluation A: 40 seconds, Evaluation B: 60 seconds, C: 90 seconds or more or insufficient curing (fair to poor). Developability - Immersed in 3% sodium silicate (JIS No. 3) aqueous solution, judged by ease of development and presence or absence of development residue. Ink receptivity (ink adhesion) and transferability (ink transferability to rubber ranking) - Using a Heidelberg two-color printing machine, depending on the quality of the printed matter and the number of sheets with paper loss (print loss that occurs at the start of printing). judgement. Rating A - Excellent visual test results for printed matter and tearing of 20~
Approximately 30 sheets, Rating B - Visual test result of printed matter is good, number of torn sheets is approximately 30-50. IPA dampening water resistance - Using a commercially available dampening water containing IPA (isopropyl alcohol), the swelling property of the plate surface and the condition of the plate surface after printing 50,000 sheets were evaluated. UV ink resistance - A commercially available UV curable ink was used and the condition of the plate surface was examined and the rating C was rated as unacceptable. Printing durability - Rating A - Printing can be maintained for more than 200,000 sheets. Rating B - 100,000 to 200,000 is the limit, Rating C - 100,000 or less. Example 8 (Copolymer) Poly(styrene-CO-monoisopropyl maleate) (molar ratio 2:1) 70 parts (Copolymer) Poly(tert-butyl methacrylate-CO-methyl methacrylate-CO-methacrylic acid) Reference Example 2
Synthetic product (molar ratio 7:2:1) 30 parts (Crosslinking agent) Triethylene glycol diacrylate 10 parts Trimethylolethane triacrylate 50 parts (Photoactive agent) p・p′-bis(dimethylamino)thiobenzophene Non 3 parts Benzoin isopropyl ether 6 parts (thermal polymerization inhibitor) p-methoxyphenol 0.01 part (surfactant) Polyoxyethylene sorbitan monolaurate
0.5 parts (colorant) CI Solvent Blue 73 1 part Dissolve the above in 680 parts of methyl cellosolve,
A photosensitive solution of 28 cps (25°C) was prepared. By using a spinner (rotary coating machine) to apply the photosensitive liquid
Coat it on a polyimide film-based 35μ copper foil-covered flexible board at 1000 rpm, dry at 70℃,
A photosensitive layer of 5μ was formed. The surface of the copper foil was degreased with 1,1,1-trichloroethylene, treated with 3% hydrochloric acid, and washed with water in a conventional manner. Photosensitive layer and test pattern (manufactured by Toppan Printing,
TOPAN RESOLUTION TEST TARGET) is placed in close contact with the mask alignment device (Kyowa Riken, light source ultra-high pressure mercury lamp 100V, 250W, exposure area 60
mmφ) for 3 seconds. The exposed flexible substrate was immersed in a 0.5% sodium carbonate aqueous solution, processed at 20°C for 2 minutes, developed, washed with water, and 3%
After rinsing with phosphoric acid and rinsing with water again, a negative image of the test pattern was obtained on the copper foil. After corroding the copper foil with 40Be' ferric chloride aqueous solution, it was immersed in a 5% caustic soda aqueous solution at 25° C. for 5 minutes, and the photocured portion was peeled off and washed with water. The copper pattern had sufficient resolution for a line width of 7 μm and had good edge sharpness. Comparative Example 3 In the photosensitive liquid composition of Example 8, 30 parts of poly(methyl methacrylate-CO-methacrylic acid (molar ratio 8.3:1.7) was used instead of the copolymer, the other compositions were kept the same, and the viscosity was 28 cps. A photosensitive solution was prepared at (25°C). A photosensitive layer was formed on a flexible substrate under the same conditions as in Example 8 to obtain a film with a thickness of 5.5 μm. When exposed using the same equipment as in Example 8, the result was sufficient. It was learned that 15 to 20 seconds of exposure is required for proper photocuring to occur. Example 9 (Copolymer) Poly(styrene-CO-monoethyl maleate)
(Molar ratio 1.5:1) 45 parts (Copolymer) Poly(tert-butyl methacrylate-CO-methyl methacrylate-CO-methacrylic acid) (Molar ratio 7:2:1) 55 parts (Crosslinking agent) p・p'- Bis(azido)benzophenone 12 parts (photoactive agent) Thioxanthone 5 parts (surfactant) Florado FC430 (fluorinated surfactant manufactured by Sumitomo 3M) 0.5 parts (colorant) CI Solbend Blue 3 1 part Add the above to ethyl cellosolve Dissolved in 540 parts,
A 24 cps (25°C) photosensitive solution was prepared. In the same manner as in Example 8, a photosensitive liquid was applied to a polyimide-based flexible substrate and dried to form a photosensitive layer having a thickness of 2 μm. Example 8: Print a test pattern for 1 second using a mask alignment device
Using the same process as above, a copper pattern with a line width of 10μ was resolved. Example 10 (Copolymer) Poly(styrene-CO-monoisopropyl maleate) (molar ratio 1:1) 40 parts (Copolymer) Poly(isobutyl methacrylate-CO-methyl methacrylate-CO-methacrylic acid) ( Molar ratio 6:
2:2) 60 parts The above copolymer was dissolved in 150 parts of butyl acetate and kneaded with 96 parts of carbon black using three rolls to obtain a pigment dispersion. Said pigment dispersion 50 parts (Crosslinking agent) Trimethylolpropane triacrylate 6 parts Tetraethylene glycol diacrylate 6 parts (Photoactive agent) Benzophenone 4 parts p・p'-bis(diethylamino)benzophenone
0.5 part (thermal polymerization inhibitor) Kyuferon 0.01 part (surfactant) Polyoxyethylene sorbitan monolaurate
Add 0.6 parts of the above mixture to a mixed solution of 25 parts of methyl cellosolve and 20 parts of methyl cellosolve acetate,
A uniform pigment dispersion of 150 cps (25°C) was obtained. The pigment dispersion was coated on a biaxially stretched polyethylene terephthalate film (75μ thick) with a roughened surface using a φ0.4mm wire bar coater and dried at 70°C to produce a black photosensitive film with a dry film thickness of 5μ. . Closely expose a test pattern to a photosensitive film and use an ultra-high pressure mercury lamp (3kW) at a distance of 80cm.
Light was irradiated for 60 seconds (intensity 6.5 mw/cm ² ). After developing the exposed photosensitive film by immersing it in a 0.5% ethanolamine aqueous solution for 30 seconds at 20°C,
The residue was removed by spray cleaning with a water pressure of Kg/cm ² and dried to obtain a black image. This image is used as an original map for map engraving and screen printing, and the matte surface of the base film exposed in the non-exposed area has a surface marking property. The density of the above image was measured and the following values were obtained.

[Table] (Using a densitometer manufactured by Macbeth, USA)
In addition, the image was resolved as a circle with a diameter of 50μ and a line with a line width of 50μ.

Claims (1)

[Scope of Claims] 1 A copolymer composed of two types of monomers represented by the general formula () (CH ₂ = CHAr) _n1 ·(HOOCCH = CHCOOR ₁ ) _n2 …………() [However, , in the formula (), Ar represents a phenyl group or a substituted phenyl group, R represents a lower alkyl group, and the numbers m ₁ and m ₂ represent the abundance ratio of each monomer in the copolymer, m ₁ ≧ m ₂ . ] and a copolymer composed of three types of monomers represented by the general formula () [CH ₂ =C(R ₂ )COOR ₃ ] _o1・[CH ₂ =C(R′ ₂ )COOR ₄ ] _o2・[CH=C(R″ ₂ )COOH] _o3 ………() [However, in formula (), R ₂ , R′ ₂ , and R″ ₂ are hydrogen atoms or methyl groups, and R ₃ is methyl groups or Ethyl group, R ₄
represents an isobutyl group or a tertbutyl group, and the numbers n ₁ , n ₂ , and n ₃ represent the abundance ratio of each monomer in the copolymer, and n _1kiO , n _2kiO , (n ₁
+ _n2 ) _/n3=0.5~20 . ] A photocurable photosensitive material characterized by simultaneously containing two types of copolymerized polymer compounds, and containing appropriate amounts of a crosslinking agent and a photoactivator.