JPH0136482B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photosensitizing polymer that provides a photoinsolubilizable resin with excellent photosensitivity and a method for producing the same. More specifically, the present invention relates to a photosensitizing polymer having a dialkylaminoketone as a photosensitizing residue in a side chain. Many studies have been conducted to increase the photosensitivity speed of photoinsolubilizable resins based on the principle of photopolymerization, and most of them are related to photopolymerization sensitizers (initiators) active to ultraviolet rays. On the other hand, photosensitive resin
Beyond photoresist materials, inks, paints, varnishes, printing plate materials, etc., it is attracting attention as an image-forming material that uses laser light and a photosensitive material that replaces silver salt, but the photosensitive characteristics of this new material are different from those of conventional materials. However, it is still 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. Japanese Patent Publication No. 1973-36281
In this issue, S-- having at least one trihalomethyl group conjugated to a triazine ring due to ethylenic unsaturation and at least one chromophore moiety
A method using triazine as a polymerization initiator has been proposed. In addition, in JP-A-54-15529, p-
A composition using an unsaturated ketone conjugated with dialkylaminoallylidene as a photopolymerization initiator has been proposed. 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 sensitivity to be used as laser-sensitive materials or silver salt substitute materials. Speed is desired. The photosensitivity speed of a photoinsolubilized resin is determined by 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. The polymer composition that is sensitive to visible light is characterized by a low-molecular photopolymerization initiator that absorbs visible light, so it can be said that it aims to achieve high sensitivity by focusing on the absorbance of the photosensitive group. I can do it. As a result of careful consideration of the above points, the present inventor found that by polymerizing the photopolymerization initiator that absorbs visible light, it is possible to achieve even higher sensitivity, and because the resin is homogeneous, high resolution can be achieved. We believe that this can also be expected, and have thus come up with the present invention. That is, the present invention is based on the general formula (In the formula, R ₁ represents a hydrogen atom or a methyl group,
R ₂ is -CO-, -COOCH ₂ CH(OH)CH ₂ - or

It is a divalent organic residue selected from [Formula], R ₃ represents a C ₁ to _{C 3} lower alkyl group, and n represents 1 or 2) having an aminophenyl ketone derivative represented by 2
~20 mol% vinyl units and general formula (In the formula, R ₁ has the same meaning as above, and R ₄ represents an alkoxycarbonyl group, a carbamoyl group, or a nitrile group.) Molecular weight 5000~1000000
This invention relates to a vinyl photosensitizing polymer compound and a method for producing the same. According to the present invention, by bonding a photosensitive residue having the ability to initiate photopolymerization to a polymer, the initiation site itself directly participates in the insolubilization of the polymer by radical polymerization, resulting in even higher sensitivity. is achieved. Among the structures represented by general formula (), n=1
In this case, unsaturated ketone residues such as arylideneacetonephenone easily undergo a photodimerization reaction to form cyclobutane when irradiated with light.
A polymer having this residue in its side chain already has photoinsolubilization ability. However, p-dialkylamino substituted derivatives have lower photodimerization ability than unsubstituted derivatives. Therefore, although a polymer having a structural unit of the general formula () itself exhibits photoinsolubilization ability, its efficiency is not good. However, as will be described later, by mixing other auxiliary substances with the polymer of the present invention together with a substance capable of vinyl polymerization, a significantly highly sensitive photoinsolubilization ability will be exhibited. In order to produce the polymer compound of the present invention having these 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 is that it is easily available (meta)
It focuses on the reactivity of the epoxy group of glycidyl acrylate, and the raw material is a copolymer of this reactive vinyl monomer and other copolymerizable vinyl monomers. The compound required to introduce the photosensitizing residue has the general formula: (In the formula, R ₃ and n have the same meanings as above.) It is an aminoketone having a phenolic hydroxyl group. Among the compounds represented by the general formula (), when n=1 or 2, it is easily produced by a dehydration condensation reaction between the alkyl-substituted product and a p-dialkylamino-substituted aromatic aldehyde. The reaction between the compound represented by the general formula () and the glycidyl (meth)acrylate copolymer is carried out in a polar solvent. Solvents that do not have 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, the addition of halogen ions is extremely effective, and for this purpose, lithium chloride, lithium bromide, tetraethylammonium chloride,
Halides such as tetraethylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, triethylbenzylammonium chloride, and triethylbenzylammonium bromide are used, and organic ammonium chloride is particularly 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. Reaction temperature ranges from room temperature
A range of 100°C is used, preferably a range of 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 and precipitating it. The resin obtained in this way has the general formula (R ₁ , R ₃ and n in the formula have the same meanings as above)
It is a polymer containing a photosensitizing structural unit represented by Compounds 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, benzyl methacrylate, 2-ethylhexyl methacrylate,
N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-vinylpyrrolidone,
Examples include 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 molar ratio of these vinyl comonomers and glycidyl (meth)acrylate may be in any range from 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 a significantly low sensitizing ability. A second method for producing a polymer containing a vinyl unit 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 ₃ and n in the formula have the same meanings as above) is produced. Examples of the polymer having active halogen atoms used in this reaction include chloromethylstyrene polymers or copolymers. 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 metal salt using a strong alkali, and this is reacted with a halogen-containing molecule in a polar solvent. Preferred polar solvents used here include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and dichlorobenzene. The reaction temperature is conveniently between room temperature and 120°C. The reaction time is about 1 hour 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 transfer method such as an organic ammonium salt or sulfonium salt may be used. The reaction may be carried out in a two-phase system of an organic solvent and water using a 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 reality, 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 the product from gelling 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 preferred. A third method for producing a polymer containing a side chain having photosensitizing ability represented by the general formula () will be described next. This method differs from the first two methods in that a vinyl monomer containing a photosensitizing residue is prepared in advance and other vinyl monomers are copolymerized therewith. The vinyl monomer containing a photosensitizing residue used here has the general formula () (In the formula, R ₁ , R ₃ , and n have the same meanings as above.) Examples include, but are not limited to, the following: These vinyl monomers can be easily converted into unsaturated ketones having a phenolic hydroxyl group represented by the general formula () by acylating them with (meth)acrylic acid chloride or by vinylbenzylating them with chloromethylstyrene. Can be 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, acrylamide, etc. These vinyl monomers can be used alone or in combination. As the copolymerization method used here, a commonly used method can be used as is, but 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 excellent 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 slow insolubilization rate when irradiated with light when used alone, but it transfers one electron with the photosensitive group represented by the general formula () when irradiated with light. By coexisting with a compound that generates radical species, it becomes a highly efficient photopolymerization initiation system. The one-electron-reduced compounds used for this purpose are electron-accepting; examples include ketone or quinone compounds such as benzophenone, benzoquinone, naphthoquinone, anthraquinone, benzanthrone, fluorenone, diphenyliodonium salts, ditolyliodonium salts. , iodonium salts such as di(m-nitrophenyl)iodonium salts, 2,4,6-tris(trichloromethyl)-S-triazine, 2-methyl-
S-triazine derivatives such as 4,6-bis(trichloromethyl)-S-triazine, 2-phenyl-4,6-bis(trichloromethyl)-S-triazine, p-nitro-α,α,α-tribromo Trihaloacetylated benzene derivatives such as acetophenone, O-nitro-α,α,α-tribromoacetophenone, α,α,α-tribromoacetophenone, tribromomethanesulfonylbenzene,
Examples include benzene derivatives having a trihalomethanesulfone group such as 1-tribromomethanesulfonyl-3-nitrobenzene, and triphenylbisimidazolyl. These electron-accepting compounds can be mixed in an amount of 0.5 to 1.0 molar equivalent, more preferably 1 to 5 molar equivalent, with respect to the photosensitive residue represented by the general formula (), to achieve highly efficient photopolymerization. Becomes a starting system. 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 high molecular weight compounds. But that's fine. Specifically, acrylic acid,
High-boiling monomers include methacrylic acid, crotonic acid, itaconic acid, maleic acid, acrylamide, methacrylamide, diacetone acrylamide, N-vinylcarbazole, as well as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. , 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-
Di- or polyacrylic esters such as decanediol, trimethylolethane, pentaerythritol, sorbitol, mannitol, di- or polymethacrylic esters, as well as acrylated or methacrylated epoxy resins, polyester acrylate oligomers, acrylated or methacrylated Examples include urethane oligomers and acroleinated polyvinyl alcohol. 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 need 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, thereby generating a radical cation represented by the following partial structural formula. This is thought to be because protons are detached from the alkyl group (R ₃ ), and the resulting radicals initiate polymerization, resulting in 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 of the reasons why the resin composition of the present invention exhibits high sensitivity. Pigments or dyes may be added as colorants to the photoinsoluble resin composition of the present invention, if desired. Furthermore, leuco dyes such as leucomalachite green, leuco crystal violet, etc. may be added to develop color using generated radicals. In this case, the visible coloring produced by light irradiation is particularly convenient for plate-making operations. Suitable light sources for the composition of the present invention include high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon lamps, halogen lamps, fluorescent lamps, as well as He-Cd lasers and Ar
Laser available. The photoinsolubilized 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,
It can be applied to a wide range of fields such as creating reliefs, creating non-silver halide images, and creating printed wiring boards, and because it is sensitive to laser light, it is also effective for negative plate making. By way of example below,
This will be explained in more detail. Example 1 9.8 g of potassium hydroxide was dissolved in 35 g of ethanol, and p-dimethylaminobenzaldehyde was added to the solution.
14.9 g and 13.6 g of p-acetylphenol were added and dissolved, and the mixture was reacted under reflux for 3 hours. Next, ethanol was distilled off under reduced pressure to concentrate the reaction solution, and this was poured into 500 ml of water. 4-
Dimethylamino-4′-hydroxychalcone 18.8g
(yield 70%). Melting point 219-220°C 4-diethylamino-4'-hydroxychalcone and (p-dimethylaminocinnamylidene)-4-hydroxyacetophenol were obtained in the same manner. Example 2 95:5 copolymer of methyl methacrylate and glycidyl methacrylate (w=2.64×10 ⁵ , n=
1.77×10 ⁵ ) was dissolved in 18 g of dimethylacetamide, and 0.108 g of tetrabutylammonium chloride was further added. Add 0.262 g of 4-dimethylamino-4'-hydroxychalcone to this solution,
The mixture was stirred at room temperature for 30 minutes to dissolve, and then heated at 80°C for 5 hours. Pour the reaction solution into 250 ml of methanol to precipitate and separate the polymer, then add it again to chloroform.
Dissolved in 20g. This was poured into 200 ml of methanol and reprecipitated. The separated resin was thoroughly washed with methanol and then vacuum dried at 50°C to obtain 1.76 g of a yellow polymer. 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 10wt% of the polymer was dissolved.
p-xylylene dimethacrylate was added thereto, and benzanthrone was further added as an auxiliary substance to prepare a photosensitive solution. This solution was spin-coated onto an anodized aluminum plate by Kodak Photographic Co., Ltd.
It was irradiated with a xenon lamp for 1 minute through Steptablet 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. Since commercially available polyvinyl cinnamate photosensitive materials undergo two-step insolubilization after 40 seconds of exposure, it can be seen from the results in Table 1 that they exhibit approximately the same sensitivity.

[Table] To the ethyl cellosolve acetate solution of the polymer thus obtained, benzantrone was added in an amount equivalent to 2 moles relative to the photosensitive group of the polymer, and p-xylylene dimethacrylate was added in varying amounts to form a photosensitive solution. did. 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 (w=2.08×10 ⁵ ,
n=1.09×10 ⁵ ) 2g dimethylacetamide 11
Tetrabutylammonium chloride dissolved in g
Added 0.62g. In this, 4-dimethylamino-
Add 0.75g of 4'-hydroxychalcone and stir at room temperature for 30 minutes.
After stirring for several minutes to dissolve, the mixture was 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. Place the separated polymer in chloroform 20
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. This is a dimethylaminochalcone residue, which is a photosensitive group, according to the ultraviolet absorption spectrum.
It became clear that it contained 10.7 mol%. The sensitivity of the photosensitive resin composition prepared by adding benzanthrone and p-xylylene dimethacrylate to the thus obtained polymer was measured in the same manner as in Example 3. The obtained results are summarized in Table 3. This result means that the sensitivity is approximately 15 times higher than that of polyvinyl cinnamate-based photosensitive materials.

[Table] Example 4 In Example 2, 4-dimethylamino-4'-
A similar reaction was carried out using 0.28 g of 4-diethylamino-4'-hydroxychalcone instead of hydroxychalcone. Separated and purified yellow polymer 1.80
The ultraviolet absorption spectrum showed that g contained 1.6 mol% of photosensitive groups. A photosensitive resin composition prepared by adding 50 wt% of p-xylylene 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 4 stages were insolubilized. Example 5 In Example 2, 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-xylylene dimethacrylate to this polymer and further adding 2 molar equivalents of benzanthrone to the photosensitive group was evaluated for photosensitivity in the same manner as in Example 1. As a result,
Insolubilization was achieved up to 6 stages. Example 6 Methyl methacrylate-chloromethylstyrene
93:7 copolymer (w=6.15×10 ⁵ , n=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. The reaction solution was poured into 800 ml of methanol to precipitate the polymer, which was thoroughly washed with methanol and vacuum dried at 40°C to obtain 11.70 g of yellow polymer. Ultraviolet absorption spectra revealed that it contained 5.5 mol% photosensitive groups. 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 photosensitive groups introduced was obtained. Example 8 Methyl methacrylate-chloromethylstyrene
80:20 copolymer (Mw=2.48×10 ⁵ , Mn=8.81×
10 ⁴ ) 10g was dissolved in 190g of dimethylacetamide, 8.28g of potassium salt of 4-dimethylamino-4'-hydroxychalcone was added thereto, stirred at room temperature for 20 minutes, and then reacted at 65°C for 5 hours. . The reaction solution is poured into 1.8 methanol to precipitate the polymer, washed with methanol, and then vacuum dried at room temperature. The obtained polymer was dissolved in tetrahydrofuran.
This solution was filtered to remove insoluble materials, and then reprecipitated into methanol. This was thoroughly washed with methanol and vacuum dried at 40°C to obtain 13.74 g of yellow polymer. It was revealed from the ultraviolet absorption spectrum that 11.6 mol% of photosensitive groups were introduced. Example 9 PEG400DA (CH ₂ =CHCO ₂ (-CH ₂ -
CH ₂ O) - ₉ OCCH=CH ₂ ) and auxiliary substances were added and spin-coated onto an anodized aluminum plate and coated with Kodak Photographic as in Example 3.
It was exposed for 5 seconds to a xenon lamp through a Steptablet No. 1A and then developed for 15 seconds with dimethylacetamide. Table 4 summarizes the results of expressing sensitivity by the number of insolubilized plates. Diphenyliodonium hexafluorophosphate and 2-methyl-4,6-bis(trichloromethyl)-S-triazine were used as electron-accepting auxiliary substances. The sensitivity shown in the 7th step in this table corresponds to about 128 times that of polyvinyl cinnamate light-sensitive materials.

[Table] Example 10 20g of 4-dimethylamino-4'-hydroxychalcone obtained in Example 1 was added to 260g of tetrahydrofuran.
Dissolve ethyl diisobutylamine in this 8.5
g was added. While stirring at room temperature, 8.6 g of methacrylic acid chloride was added dropwise, and after 5 hours had passed, 2.1 g of ethyldiisobutylamine was added.
Add 2.3g of methacrylic acid chloride dropwise to 12
Stirring was continued for an hour. 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. 18.6 g of 4-dimethylamino-4'-methacryloyloxychalcone was obtained by recrystallization from methanol.
(yield 69%). Melting point 98-100℃. Example 11 1.5 g of 4-dimethylamino-4'-methacryloyloxychalcone and 14.55 g of methyl methacrylate
Dissolved in 81g of benzene in a 200ml Erlenmeyer flask,
Furthermore, 81 mg of azobisisobutyronitrile was added. The inside of the flask was purged with high-purity argon, then sealed, and reacted at 50°C for 50 hours. The polymerization solution was poured into n-hexane, the resulting precipitate was washed with n-hexane, and then dried under reduced pressure at 40°C to obtain 12.5 g (yield: 78%) of a yellow polymer. Results of analysis by ultraviolet absorption spectrum
It was revealed that 3.5 mol% of photosensitive groups were introduced. Examples 12, 13 In the same manner as in Example 11, 4-dimethylamino-
By changing the charging ratio of 4'-methacryloyloxychalcone and methyl methacrylate, polymers with different photosensitive group introduction ratios were obtained. The results of Example 11 are also shown in Table 5.

【table】

[Table] Example 14 Photosensitive compositions having the compositions shown in Table 6 were prepared using the methyl methacrylate photosensitizing polymers obtained in Examples 11 to 13. As an auxiliary substance,

[Table] Compositions were prepared using diphenyliodonium hexafluorophosphate, 2-methyl-4,6-bis(trichloromethyl)-S-triazine, and benzanthrone in varying molar equivalents relative to the photosensitizing residue. Added. The photosensitive solution formulated in this way was applied to an anodized aluminum plate at a rotation speed of 400 rpm, and Kodak Photographic
Place Steptablet No.1A and use xenon lamp 2
Second exposure. This was developed by immersing it in N,N-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 with 20 seconds exposure and 3 stages with 40 seconds exposure. Therefore, compared to this commercially available photosensitizer, diphenyliodonium salt has
2.5 to 40 times, 2.5 in the case of 2-methyl-4,6-bis(trichloromethyl)-S-triazidine
This means that it is ~40 times more sensitive, and up to 10 times more sensitive in the case of benzantrone.

[Table] Examples 15-17 Put 0.201 g of 4-dimethylamino-4'-methacryloyloxychalcone, 1.33 g of n-butyl methacrylate, and 7.68 g of benzene into a 10 ml ampoule tube, and add 7.7 mg of azobisisobutyronitrile. Added. After repeating freezing, degassing, and argon gas replacement three times, the tube was sealed under reduced pressure. After shaking this ampoule tube at 50°C for 48 hours, the polymerization solution was poured into hexane. The resulting precipitate was washed with hexane and then vacuum dried at 40°C. 1.256 g (82% yield) of yellow polymer was obtained. The amount of photosensitive groups introduced at this time was 6 mol%, but analysis by ultraviolet absorption spectrum revealed that 5.8 mol% of photosensitive groups had been introduced. Polymers having different photosensitive group introduction ratios were obtained in the same manner by varying the charging ratio of 4-dimethylamino-4'-methacryloyloxychalcone and n-butyl methacrylate. The above results are summarized in Table 8.

[Table] Example 18 Based on Example 11, methyl methacrylate-based photosensitizing polymer (
w = 2.99 × 10 ⁵ , n = 1.11 × 10 ⁵ ) was synthesized, and to this methyl cellosolve solution was added benzanthrone as an auxiliary substance in an amount of 2 molar equivalents based on the photosensitive group.
Furthermore, various vinyl polymerizable compounds were added in the proportions shown in Table 9 to prepare a photosensitive composition. The photosensitivity of this photosensitive solution was evaluated in the same manner as in Example 14. However, the exposure time was 5 seconds, and methyl cellosolve was used as the developer. The results are summarized in Table 9.

【table】

[Table] Example 19 Two molar equivalents of diphenyliodonium hexafluorophosphate and 50 wt% PEG400DA were added to the n-butyl methacrylate photosensitizing polymer obtained in Examples 15 to 17 based on the photosensitive group. The added sensitivity was evaluated. The sensitivities exhibited by the methyl methacrylate polymers obtained in Examples 11 to 13 are summarized in Table 10 for comparison.

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ represents a hydrogen atom or a methyl group,
R ₂ is a divalent organic residue selected from -CO-, -COOCH ₂ CH(OH)CH ₂ - or [Formula], R ₃ represents a C ₁ to C ₃ lower alkyl group, and n indicates 1 or 2) 2 with an aminophenyl ketone derivative represented by
~20 mol% vinyl units and general formula (In the formula, R ₁ has the same meaning as above, and R ₄ represents an alkoxycarbonyl group, a carbamoyl group, or a nitrile group.) Average molecular weight 5000~1000000
Vinyl photosensitizing polymer compound. 2 General formula (In the formula, R ₃ represents a lower alkyl group of 1 to 3,
A general formula characterized by reacting an aminoketone having a phenolic hydroxyl group represented by (n represents 1 or 2) with a copolymer containing glycidyl (meth)acrylate as one component. (In the formula, R ₁ represents a hydrogen atom or a methyl group,
R ₂ is -COOCH ₂ CH(OH)CH ₂ -, R ₃ ,
2 having an aminophenyl ketone derivative represented by (n has the same meaning as above)
~20 mol% vinyl units and general formula (In the formula, R ₁ has the same meaning as above, and R ₄ represents an alkoxycarbonyl group, a carbamoyl group, or a nitrile group.) Average molecular weight 5000~1000000
A method for producing a vinyl photosensitizing polymer compound. 3 General formula (In the formula, R ₃ is a C ₁ to C ₃ lower alkyl group,
A general formula characterized by reacting an aminoketone having a phenolic hydroxyl group represented by (n represents 1 or 2) with a chloromethylstyrene (co)polymer. (In the formula, R ₁ represents a hydrogen atom or a methyl group,
R ₂ is [Formula], and R ₃ , n have the same meanings as above) 2 having an aminophenyl ketone derivative represented by
~20 mol% vinyl units and general formula (In the formula, R ₁ has the same meaning as above, and R ₄ represents an alkoxycarbonyl group, a carbamoyl group, or a nitrile group.) Average molecular weight 5000~1000000
A method for producing a vinyl photosensitizing polymer compound. 4 General formula (In the formula, R ₁ is a hydrogen atom or a methyl group,
R ₂ represents -CO-, R ₃ represents a C ₁ to _{C 3} lower alkyl group, and n represents 1 or 2). (In the formula, R ₁ has the same meaning as above, and R ₄ represents an alkoxycarbonyl group, a carbamoyl group, or a nitrile group.) , general formula (In the formula, R ₁ , R ₂ , R ₃ , and n have the same meanings as above)
~20 mol% vinyl units and general formula (In the formula, R ₁ and R ₄ have the same meanings as above) Consisting of 98 to 80 mol% (meth)acrylic vinyl units with a weight average molecular weight of 5,000 to 1,000,000
A method for producing a vinyl photosensitizing polymer compound.