JPH0315921B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photoinsoluble resin composition that exhibits excellent photosensitivity, and more specifically, a photopolymerizable resin that contains a polymer having a photosensitive group in its side chain that can generate radicals when irradiated with light. The present invention relates to a composition. Many studies have been conducted to increase the photosensitivity speed of photoinsoluble resins based on the principle of photopolymerization, and most of them are related to photopolymerization sensitizers (initiators) that are active to ultraviolet light. On the other hand, photosensitive resins are attracting attention not only as photoresist materials, inks, paints, varnishes, and printing plate materials, but also as image-forming materials that use laser light and photosensitive materials that replace silver salts. The photosensitive properties of conventional materials are extremely inadequate. Therefore, it is necessary to expand the photosensitive wavelength range and dramatically increase the photosensitive speed. In this case, it goes without saying that the photosensitive resin must have both high resolution, which is an excellent characteristic, and various physical properties suitable for the purpose. Several proposals have been made for photopolymerizable resins that are sensitive to visible light. In JP-A-48-36281, S having at least one trihalomethyl group conjugated to a triazine ring through ethylenically unsaturation and at least one chromophore moiety is disclosed.
- A method using triazine as a polymerization initiator has been proposed. Furthermore, Japanese Patent Application Laid-Open No. 15529/1984 proposes a composition using an unsaturated ketone conjugated with p-dialkylaminoallylidene as a photopolymerization initiator. Alternatively, JP-A-52-134692 proposes a composition using a polycyclic quinone and a tertiary amine as a photopolymerization initiation system. All of these can provide materials that are sensitive to longer wavelengths than conventional photopolymerizable resins, but they require even higher photosensitive speeds to be used as photosensitive materials for lasers, silver salt substitute materials, etc. is desired. The photosensitivity of a photoinsolubilized resin depends on the molecular weight of the polymer to be insolubilized, the efficiency of the crosslinking reaction necessary for photoinsolubilization,
and the absorbance of the photosensitive group. Since the above-mentioned polymer composition sensitive to visible light is characterized by a low-molecular photopolymerization initiator that absorbs visible light, it can be said that high sensitivity was achieved by focusing on the absorbance of the photosensitive group. I can do it. As a result of careful consideration of the above points, the inventors of the present invention found that it is possible to achieve even higher sensitivity by polymerizing a photopolymerization initiator that absorbs visible light.
The present invention was developed based on the idea that high resolution can be expected because the resin is homogeneous. That is, the present invention provides (A) general formula () (In the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group, or a lower alkoxy group, R ₃ is a lower alkyl group, and n is 1 or 2.) Molecular weight 5000~ containing at least one sensitive residue in the side chain
1 part of a photosensitizing polymer compound in the range of 1,000,000, and (B) 0.01 to 0.5 parts of at least one compound selected from the group of compounds that generate radical species by being reduced by one electron. , (C) at least one compound selected from the group of compounds having at least one ethylenically unsaturated bond having polymerization ability 0.1~
The present invention provides a photoinsoluble resin composition characterized in that it consists of 5 parts. According to the present invention, by linking a photosensitive residue having a photopolymerization initiator to polymerization, the initiation site itself directly participates in the insolubilization of the polymer by radical polymerization, resulting in even higher sensitivity. is achieved. Since the structure represented by the general formula () causes a dimerization reaction when irradiated with light, the polymer having this residue in its side chain already has photo-insolubilization ability. However, its photosensitivity is not sufficiently high, and by using it together with other auxiliary substances and a substance capable of vinyl polymerization according to the present invention, it exhibits a photoinsolubilizing ability with extremely high sensitivity. In order to produce the polymer compound (A) constituting the photoinsoluble resin composition of the present invention having such characteristics, it is necessary to efficiently polymerize this relatively large molecular weight residue. The following three methods are particularly effective for this purpose, and will be explained in detail below. The first method focuses on the reactivity of the epoxy group of glycidyl (meth)acrylate, which is easily available, and involves copolymerizing this reactive vinyl monomer with other copolymerizable vinyl monomers. Polymer is the raw material. The compound necessary to introduce the photosensitizing residue has the general formula () It is an aminoketone having a phenolic hydroxyl group represented by the formula (wherein R ₁ , R ₂ , R ₃ , and n have the same meanings as above). The compound represented by the general formula () is easily produced by a dehydration condensation reaction between acetylphenols and p-dialkylaminobenzaldehydes. The reaction between the compound represented by the general formula () and the glycidyl (meth)acrylate copolymer is carried out in a polar solvent. As a solvent, a solvent without active hydrogen, such as tetrahydrofuran, acetonitrile, acetone, chloroform, trichlene,
O-dichlorobenzene, dimethylformamide,
dimethylacetamide, N-methylpyrrolidone,
Dimethyl sulfoxide is preferred. In order to accelerate this reaction, it is effective to add halogen ions, and for this purpose, halogen ions such as lithium chloride, lithium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, triethylbenzylammonium chloride, etc. chemical substances are used,
Among them, organic ammonium chloride is preferred. A phenol derivative represented by the general formula () is used in an amount ranging from equivalent to 10 times the molar amount based on the glycidyl (meth)acrylate unit, and a halide as a catalyst is added to the phenol derivative based on 1 part of the phenol derivative.
It is added in the range of 0.01 part to 0.5 part and reacted in the above polar solvent. The reaction temperature used is from room temperature to 100°C, preferably from 40 to 80°C. Further, the reaction time varies depending on the reaction temperature and the amount of catalyst, but is usually 1 hour to 20 hours. Continuing the reaction at an unnecessarily high temperature and for a long time should be avoided since this may cause unnecessary thickening or insolubilization of the reactants. The reaction product can be purified by pouring into a poor solvent to precipitate it. The resin obtained in this way has the general formula () due to the reaction between the phenolic hydroxyl group and the epoxy group. (In the formula, R ₁ , R ₂ , R ₃ , and n have the same meanings as above, and R ₄ is a hydrogen atom or a methyl group). Examples of the compound having a phenolic hydroxyl group represented by the general formula () used in this reaction include, but are not limited to, the following. In addition, vinyl monomers used in the copolymer of glycidyl (meth)acrylate reacted with these compounds include acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate,
2-ethylhexyl acrylate, benzyl acrylate, acrylic acid, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzine methacrylate, 2-ethylhexyl methacrylate, N,N-dimethylacrylamide, N,N-
Examples include dimethylmethacrylamide, N-vinylpyrrolidone, styrene, 2-vinylpyridine, and 4-vinylpyridine. It goes without saying that only one type of these vinyl comonomers may be used, or a plurality of types may be used. In this case, the copolymerization ratio of these vinyl comonomers and glycidyl (meth)acrylate may be any in the range of 20:80 to 98:2. If the ratio of the comonomer is smaller than this, the storage stability of the resulting photosensitized polymer will be poor,
On the other hand, if it is larger than this range, the rate of introduction of residues with photosensitizing ability is low, resulting in extremely low photosensitizing ability. A second method for producing a polymer containing vinyl units having photosensitizing ability represented by the general formula () will be explained next. In this method, a polymer compound having an active halogen atom is reacted with an aminoketone derivative having a phenolic hydroxyl group represented by the general formula (). This gives the general formula () A polymer having a photosensitizing structural unit represented by (R ₁ , R ₂ , R ₃ , and n in the formula have the same meanings as above) is produced. Examples of polymers having active halogen atoms used in this reaction include chloromethylstyrene polymers or copolymers, chlorovinyl acetate polymers or copolymers, and polyepichlorohydrin. In order to react these halogen-containing polymers with the phenol derivative represented by the general formula (), a strong basic substance is used as a condensing agent. That is, a phenol derivative represented by the general formula () is converted into its alkali salt using a strong alkali, and this is reacted with a halogen-containing polymer in a polar solvent. Preferred polar solvents used here include dimethylformamide, dimethylacetamide, dimethylsulfoxide, dichlorobenzene, and the like. The reaction temperature is conveniently between room temperature and 120°C. The reaction time is about 1 to 20 hours, depending on the reaction temperature and the reactivity of the halogen-containing polymer. Furthermore, in this method, an alkali salt of the compound represented by the general formula () may be reacted with a halogen-containing polymer compound in an organic solvent using a crown ether, or a phase interlayer such as an organic ammonium salt or phosphonium salt may be reacted. The reaction may be carried out in a two-phase system of an organic solvent and water using a mobile catalyst. Since the compound represented by the general formula () has an amino group, there is a possibility that quaternization may occur due to active halogen. In fact, the reactivity of this amino group is significantly reduced by ketones or conjugated ketones via the benzene ring, and quaternization hardly occurs. In order to reliably prevent gelation of the reactant due to quaternization, it is sufficient to react the compound represented by the general formula () in an amount equal to or more than the same mole relative to the active halogen group. Since it is not necessary to add too much, the range of equimolar to 5 times molar is preferable. A third method for producing a polymer having a photosensitizing residue represented by the general formula () in its side chain will be described next. This method differs from the first two in that a vinyl monomer containing a photosensitizing residue is prepared in advance, and other vinyl monomers are copolymerized with this. The vinyl monomer containing a photosensitizing residue used here has the general formula () (R ₁ , R ₂ , R ₃ , R ₄ , n in the formula have the same meanings as above, and R ₅ is -CO- or

It has the structure represented by [Formula]). Examples include, but are not limited to, the following: These vinyl monomers can be obtained by acylating an unsaturated ketone having a phenolic aquatic group represented by the general formula () with (meth)acrylic acid chloride or by vinylbenzylating it with chloromethylstyrene. It can be easily synthesized. Vinyl monomers copolymerized with these vinyl monomers having photosensitizing ability include acrylonitrile,
Methacrylonitrile, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid 2
-Ethylhexyl, benzyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, N,N-dimethylacrylamide, N,N- Examples include dimethylmethacrylamide, N-vinylpyrrolidone, styrene, 2-vinylpyridine, and 4-vinylpyridine. These vinyl monomers can be used alone or in combination. Although a commonly used copolymerization method can be used as is, a solution polymerization method is convenient in order to reliably produce a soluble polymer. All of the vinyl polymers produced by the above three methods and having a photosensitizing residue represented by the general formula () in their side chains have good storage stability. Moreover, since the copolymerization component forming the vinyl unit other than the vinyl constituent unit having photosensitizing ability can be arbitrarily selected, the polymer is characterized in that it can impart arbitrary physical properties to the polymer depending on the purpose. The polymer having a photosensitizing residue in its side chain used in the present invention has a low rate of insolubilization by light irradiation when it is used alone, but it can transfer one electron when it is combined with the photosensitive group represented by the general formula () by light irradiation. By coexisting with a compound that generates radical species, a highly efficient photopolymerization initiation system can be obtained. The one-electron-reduced compounds used for this purpose are electron-accepting and include, for example, onium salts such as diphenyliodonium, ditolyliodonium, di(m-nitrophenyl)iodonium, 2,4,6-tris( chloromethyl)-S-triazine, 2-phenyl-
S-triazine derivatives such as 4,6-bis(trichloromethyl)-S-triazine, p-nitro-
α,α,α-tribromoacetophenone, O-nitro-α,α,α-tribromoacetophenone,
Trihaloacetylated benzene derivatives such as α,α,α-tribromoacetophenone, triphenylimidazole dimer, 2-(O-chlorophenyl)
-4,5-diphenylimidazole dimer, 2-
(O-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(α-naphthyl)-4,5
- triarylimidazole dimers such as diphenylimidazole dimers, benzophenones, benzophenone derivatives such as Michler's ketone, benzoquinones, naphthoquinones, anthraquinones, 2-
Quinones such as methylacetraquinone and phenanthrenequinone, organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, and perisophthalic acid di-t-butyl ester, etc. I can do it. These electron-accepting compounds are used in an amount of 0.5 to 10 molar equivalents to the photosensitive residue represented by the general formula (),
More preferably, a highly efficient photopolymerization initiation system is obtained by mixing 1 to 5 molar equivalents. Furthermore, a chain transfer agent may be added as desired in order to increase the efficiency of the polymerization reaction by light irradiation. Examples include 2-mercaptobenzthiazole and 2-mercaptobenzoxazole. The compound having at least one ethylenically unsaturated bond having polymerization ability as the third component constituting the photoinsoluble resin composition of the present invention includes oligomers in addition to vinyl monomers, and further includes:
It may also be a high molecular weight compound. Specifically, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, acrylamide, methacrylamide,
There are high boiling point monomers such as diacetone acrylamide and N-vinylcarbazole, as well as ethylene glycol, diethylene glycol, 1,
Di or poly(meth) such as 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, trimethylolethane, pentaerythritol, sorbitol, mannitol, etc. ) Acrylic esters, further examples include (meth)acrylated epoxy resins, polyester acrylate oligomers, (meth)acrylated urethane oligomers, and acroleinated polyvinyl alcohols. The amount of these polymerizable compounds is preferably 0.1 to 5 parts based on 1 part of the photosensitizing polymer compound (A) having a photosensitive group represented by the general formula (). Furthermore, it goes without saying that these polymerizable compounds do not have to be used alone, and may be a mixture of two or more. The photoinsoluble resin composition of the present invention has the general formula ()
It becomes insolubilized at a very high rate against light at a wavelength that is absorbed by the photosensitive group represented by . This is because this photosensitive group absorbs light energy and transfers electrons to the electron-accepting compound (B), resulting in a radical cation represented by the following partial structure. It is thought that this is because ton is removed from the alkyl group _R3 , and the radicals generated thereby initiate polymerization and cause graft polymerization. Furthermore, the fact that the electron-accepting compound itself generates a radical after transferring one electron and becomes an initiator is considered to be one reason why the resin composition of the present invention exhibits high sensitivity. A pigment or dye may be added to the photoinsoluble resin composition of the present invention as a coloring agent, if desired. Furthermore, in order to develop color using generated radicals, a leuco dye such as leucomalachite green, leuco crystal violet, etc. may be added. In this case, the visible coloring produced by light irradiation is particularly convenient for plate-making work. As light sources suitable for the composition of the present invention, in addition to high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon lamps, halogen lamps, and fluorescent lamps, He-Cd lasers and Ar lasers can be used. The photoinsoluble resin composition of the present invention has superior characteristics in sensitivity and resolution than conventional photopolymerizable compositions, so it can be used as a plate-making material for planography or letterpress, for the creation of reliefs, and for non-silver salt images. It can be applied to a wide range of fields such as manufacturing and printed wiring boards, and is also effective for negativeless plate making because it is sensitive to laser light. This will be explained in more detail with reference to Examples below. Reference example Dissolve 9.8g of potassium hydroxide in 35g of ethanol,
To this, p-dimethylaminobenzaldehyde
14.9 g and 13.6 g of p-acetylphenol were added and dissolved, and the mixture was reacted under reflux for 3 hours. Then,
Ethanol was distilled off under reduced pressure to concentrate the reaction solution, and this was poured into 500 ml of water. The orange precipitate formed by adding 16 g of concentrated hydrochloric acid was collected by filtration, thoroughly washed with water, and then recrystallized from ethanol to obtain 188 g of 4-dimethylamino-4'-hydroxychalcone (70% yield). . Melting point 219-220℃. Similarly, 4-diethylamino-4'-hydroxychalcone and (p-dimethylaminocinnamylidene)-4-hydroxyacetophenone were obtained. Example 1 95:5 copolymer of methyl methacrylate and glycidyl methacrylate (Mw=2.64×10 ⁵ , Mn=
Dissolve 2g of 1.77×10 ⁵ ) in 18g of dimethylacetamide, and then add
Added 0.108g. Add 0.262 g of 4-dimethylamino-4'-hydroxychalcone to this solution and let it cool at room temperature.
The mixture was stirred for 30 minutes to dissolve, and then heated at 80°C for 5 hours. The reaction solution was poured into 250 ml of methanol to precipitate and decompose the polymer, which was then dissolved again in 20 g of chloroform. This was poured into 200 ml of methanol and reprecipitated. The separated resin was thoroughly washed with methanol and dried under vacuum at 50°C to form a yellow polymer.
Obtained 1.76g. The ultraviolet absorption spectrum revealed that this polymer contained 1.5 mol% of photosensitive dimethylaminochalcone residues. The polymer thus obtained was dissolved in ethyl cellosolve acetate, and then 10 wt.
% of p-xylylene dimethacrylate,
Furthermore, benzanthrone was added as an auxiliary substance to prepare a photosensitive solution. This solution was spray applied onto an anodized aluminum plate, irradiated with a xenon lamp for 1 minute through a Kodak Photographics Step Tablet No. 1A, and then developed with ethyl cellosolve acetate for 1 minute. Table 1 summarizes the sensitivity expressed by the number of steps of the obtained images. Commercially available polyvinyl cinnamate light-sensitive materials undergo two-step insolubilization after 40 seconds of exposure, so the results in Table 1 show that they exhibit approximately the same sensitivity. In addition, the photosensitizing polymer alone
No image appeared under these irradiation conditions.

[Table] Example 2 To the ethyl cellosolve acetate solution of the polymer obtained in Example 1, 2 molar equivalents of benzantrone to the photosensitive group of the polymer were added, and p
- Xylylene dimethacrylate was added in varying amounts to form a photosensitive solution. The sensitivity of these photosensitive compositions was similarly measured and the results are summarized in Table 2. As a result, it was revealed that by adding 50 wt % of p-xylylene dimethacrylate, the sensitivity was about 1.5 times that of polyvinyl cinnamate-based light-sensitive materials.

[Table] Example 3 80:20 copolymer of n-butyl methacrylate and glycidyl methacrylate (Mw=2.08×10 ⁵ , Mn
= 1.09×10 ⁵ ) 2g was dissolved in 11g of dimethylacetamide, and 0.62g of tetrabutylammonium chloride was added.
added. 0.75 g of 4-dimethylamino-4'-hydroxychalcone was added to this, stirred at room temperature for 30 minutes to dissolve, and then reacted at 80°C for 6 hours. The reaction solution was diluted twice with chloroform and then poured into 200 ml of methanol to precipitate the produced polymer.
Dissolve the separated polymer in 20g of chloroform,
This was poured into 200 ml of methanol and reprecipitated. The precipitated polymer was thoroughly washed with methanol and then vacuum dried at 50°C to obtain 1.63 g of yellow polymer. Ultraviolet absorption spectroscopy revealed that it contained 10.7 mol% of dimethylaminochalcone residue, which is a photosensitive group. The sensitivity of the resin composition obtained by adding benzanthrone and p-xylylene dimethacrylate to the thus obtained polymer was measured in the same manner as in Example 2. The results obtained are summarized in Table 3. This result means that the sensitivity is about 15 times that of polycinnamic acid-based photosensitive materials.

[Table] Example 4 In Example 1, 4-dimethylamino-4'-
A similar reaction was carried out using 0.28 g of 4-diethylamino-4'-hydroxychalcone instead of hydroxychalcone. The ultraviolet absorption spectrum showed that 1.80 g of the separated and purified yellow polymer contained 1.6 mol% of photosensitive groups. A resin composition in which 50 wt% of p-xylylene dimethacrylate was added to this polymer and 2 molar equivalents of benzanthro to the photosensitive group was added was subjected to sensitivity evaluation in the same manner as in Example 1. It became insolubilized. Example 5 In Example 1, 4-dimethylamino-4-
A similar reaction was carried out using 0.300 g of (p-dimethylaminocinnamylidene)-4-hydroxyacetophenone instead of hydroxychalcone. It was found that 1.83 g of the separated and purified yellow-orange polymer contained 1.5 mol% of photosensitive groups. A photosensitive resin composition prepared by adding 50 wt% of p-xylene dimethacrylate to this polymer and further adding 2 molar equivalents of benzanthrone to the photosensitive group was subjected to sensitivity evaluation in the same manner as in Example 1. As a result, up to 6 stages were insolubilized. Example 6 Methyl methacrylate-chloromethylstyrene
93:7 copolymer (Mw=6.15×10 ⁵ , Mn=1.82×
10 ⁵ ) Dissolve 10g in 90g of dimethylacetamide,
To this was added 4.12 g of potassium salt of 4-dimethylamino-4'-hydroxychalcone, stirred at room temperature for 20 minutes, and then reacted at 65°C for 5 hours. Pour the reaction solution into 800ml of methanol to precipitate the polymer.
After thorough washing with methanol, it was vacuum dried at 40°C to obtain 11.70 g of yellow polymer. Ultraviolet absorption spectra revealed that it contained 5.5 mol% of photosensitive groups. This polymer compound
PEG400DE (CH ₂ = CHCO ₂ (−CH ₂ CH ₂ O) − ₉ OCCH
= CH ₂ ) and auxiliary substances were added, spin coated onto an anodized aluminum plate, and coated with Kodak Photographic Step Tablet No. 1 in the same manner as in Example 1.
It was exposed to a xenon lamp through 1A for 5 seconds and then developed with dimethylacetamide for 15 seconds. Table 4 summarizes the results of expressing sensitivity by the number of insolubilized plates. The sensitivity shown in the 7th step in this table corresponds to about 125 times that of the polyvinyl cinnamate type sensitive material. Example 7 In Example 6, 4-dimethylamino-4'-
By performing the same operation using 4-diethylamino-4'-hydroxychalcone instead of hydroxychalcone, a polymer having 5.3 mol% of sensitive groups introduced therein was obtained. For this polymer, Example 6
Table 4 shows the results of evaluating the sensitivity of a photoreceptor having exactly the same composition as . Example 8 Methyl methacrylate-chloromethylstyrene
80:20 copolymer (Mw=2.48×10 ⁵ , Mn=8.81×
10 ⁴ ) Dissolve 10g in 190g of dimethylacetamide,
To this was added 8.28 g of potassium salt of 4-dimethylamino-4'-hydroxychalcone, stirred at room temperature for 20 minutes, and then reacted at 65°C for 5 hours. Pour the reaction solution into methanol 1.8 to precipitate the polymer,
After washing with methanol, vacuum drying was performed at room temperature. 90 g of tetrahydrofuran was added to the obtained polymer.
This solution was filtered to remove insoluble matter, and then reprecipitated into methanol. This was thoroughly washed with methanol and then vacuum dried at 40°C to obtain 13.74 g of a yellow polymer. It was revealed from the ultraviolet absorption spectrum that 11.6 mol% of photosensitive groups were introduced. Although this polymer alone exhibits only about 4 times the sensitivity of polyvinyl cinnamate-based sensitive materials, it was revealed that by preparing a photoreceptor with the same composition as in Example 6, it exhibited a maximum sensitivity of about 128 times. Summer. Table 4 summarizes the results.

【table】

[Table] Examples 9 to 11 4-dimethylamino-4'-hydroxychalcone
20g was dissolved in 260g of tetrahydrofuran, and 8.5g of ethyldiisobutylamine was added thereto. 8.6 g of methacrylic acid chloride was added dropwise while stirring at room temperature. After 5 hours, 2.1 g of amine was added, and 2.3 g of methacrylic acid chloride was further added dropwise, and the mixture was stirred for 12 hours.
The precipitated salt was filtered off, tetrahydrofuran was distilled off under reduced pressure, and the mixture was mixed with 300 ml of methylcyclohexane. A yellow-orange precipitate was formed, which was filtered off and dried under reduced pressure. By recrystallizing from methanol, 18.6 g (yield 69%) of 4-dimethylamino-4'-methacryloyloxychalcone was obtained. melting point
98-100℃. By copolymerizing the monomer thus obtained with methyl methacrylate, the copolymers shown in Table 5 were obtained.

【table】

[Table] Using the thus obtained methyl methacrylate-based photosensitizing polymer, photosensitive compositions having the compositions shown in Table 6 were prepared.

[Table] These compositions were applied to an anodized aluminum plate, a Kodatsu Photographic Step Tablet No. 1A was placed on top of the plate, and a
Second exposure. This was developed by immersing it in dimethylacetamide for 1 minute, and the sensitivity was evaluated based on the number of insolubilized plates. The results are summarized in Table 7. The obtained insolubilized film was yellow, indicating that the photosensitizing polymer itself was insolubilized. Under these exposure conditions, commercially available polyvinyl cinnamic acid photosensitizers are insolubilized up to 2 stages after 20 seconds of exposure and 3 stages after 40 seconds. Therefore, compared to this commercially available photosensitizer, diphenyliodonium salt is 2.5 to 40 times more sensitive;
-Methyl-4,6-bis(trichloromethyl)-
In the case of S-triazine, the sensitivity is 2.5 to 40 times higher, and in the case of benzantrone, the sensitivity is up to 10 times higher.

[Table] Examples 12 to 16 Methyl methacrylate-based photosensitizing polymers (Mw=2.99×10 ⁵ , Mn=1.11×10 ^{5 )} showing an introduction rate of 4.6 mol% of photosensitive groups according to Examples 9 to 11 ),
To this methyl cellosolve solution, benzanthrone was added as an auxiliary substance in an amount of 2 molar equivalents based on the photosensitive group, and various vinyl compounds were added in the ratios shown in Table 8 to prepare photosensitive compositions. The sensitivity of this photosensitive solution was evaluated in the same manner as in Examples 9-11. However, the exposure was for 5 seconds, and methyl cellosolve was used as the developer. The results are summarized in Table 8.

【table】

【table】

[Table] Examples 17-19 4-dimethylamino-4'- in a 10ml ampoule tube
0.201 g of methacryloyloxychalcone, 1.33 g of n-butyl methacrylate and 7.68 g of benzene were added, and further 7.7 mg of azobisisobutyronitrile was added. This was frozen, degassed, and replaced with argon gas three times, and then sealed under reduced pressure. at 50℃
After shaking for 48 hours, the polymerization reaction solution was poured into hexane. By changing the copolymerization ratio in the same manner, copolymers shown in Table 9 were obtained. To the thus obtained copolymer were added 2 molar equivalents of diphenyliodonium hexafluorophosphate and 50 wt% PEG400DA based on the photosensitive group, and its sensitivity was evaluated. In addition, the exposure conditions are exactly the same as Examples 9-11. The obtained results are summarized in Table 10.

【table】

【table】

Claims (1)

[Claims] 1 (A) General formula (In the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group, or a lower alkoxy group, R ₃ is a lower alkyl group, and n is 1 or 2.) Molecular weight 5000~ with at least one group in the side chain
1 part of a photosensitizing polymer compound in the range of 1,000,000, and (B) 0.01 to 0.5 parts of at least one compound selected from the group of compounds that generate radical species by being reduced by one electron. , (C) at least one compound selected from the group of compounds having at least one ethylenically unsaturated bond having polymerization ability 0.05~
5 parts of a photoinsoluble resin composition. 2 The compound that generates a radical species by one-electron reduction is a diaryliodonium salt, at least one
S-triazine compounds substituted with two mono-, di-, or trihalomethyl groups, triarylimidazole dimers, benzophenones and their nuclear substitutes, quinones, benzyl and their nuclear substitutes, and organic peroxides. The photoinsoluble resin composition according to scope 1.