JPS60112802A - Photosensitive high polymer and its preparation - Google Patents

Abstract

PURPOSE:To obtain a novel photosensitive high polymer for visible light rays, capable of providing a light-insoluble resin composition having improved sensitivity to light, by reacting a (co)polymer of chloromethylstyrene with a rhodanine derivative conjugated to a dialkylaminophenyl group. CONSTITUTION:A vinyl high polymer consisting of 1-100mol% structural unit comprising chloromethylstyrene shown by the formula I and 99-0mol% vinyl structural unit shown by the formula II (R4 is H, or CH3; R5 is phenyl, alkoxycarbonyl, etc.) is reacted with a rhodanine derivative shown by the formula III[R is single bond, or -OCO(CH2)m- (m is 1-3); R1 is H, lower alkyl, or lower alkoxy; R2 is lower alkyl; n is 0-2; M is alkali metal ion, etc.] conjugated to a dialkylaminophenyl group, to give a novel high polymer consisting of 1-30wt% photosensitive structural unit shown by the formula IV, 0-70wt% structural unit shown by the formula V (R3 is alkyl, phenyl, etc.), and 99-0wt% vinyl structural unit shown by the formula VI, having 1,000-1,000,000mol.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer sensitizer that provides a photo-soluble resin composition having excellent photosensitivity and a method for producing the same. More specifically, the present invention relates to a visible light-sensitizing polymer having a rhodanine residue conjugated with a dialkylaminophenyl group in its side chain as a photosensitizing residue, and a method for producing the same.

Many studies have been carried out to increase the photosensitivity of light-year-soluble 40{, IIH, which is based on the principle of photopolymerization, but most of them are related to photopolymerization sensitizers (initiators) that are active in ultraviolet light. be. On the other hand, photosensitive resins are attracting attention not only as photoresist materials, inks, paints, plates, and printing plate materials, but also as image-forming materials that use laser light and photosensitive materials that replace tin salts. The photosensitivity of conventional materials is extremely inadequate. Therefore, we have expanded the photosensitive wavelength range and increased the photosensitive speed to V? 11
It is necessary to increase the It goes without saying that it must also have high resolution (1'L), which is the characteristic of this photosensitive resin, and various physical properties that are 11 times better.

Several proposals have been made for photopolymerizable raw resins that are sensitive to visible light. JP-A-48-36281 proposes a method in which S-triazine having at least one trihalomethyl group conjugated to a triazine ring due to ethylenically unsaturated and at least one chromophore moiety is used as a polymerization initiator. 15529, published in Japanese Patent Publication No. 15529.
In the 2';
[[Acids have been proposed. Also, JP-A No. 511346
In Publication No. 92+1 Te, a composition using a polycyclic quinone and a tertiary amine as a photopolymerization initiation system is proposed.

All of these can provide materials that are sensitive to longer wavelength light than conventional photopolymerizable resins, but they require even higher sensitivity in order to be used as photosensitive materials for lasers or silver salt substitute materials. is necessary.

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 containing a low-molecular-weight "R" initiator that absorbs visible light. You can say it's something.

As a result of careful consideration of the above points, the present inventors have discovered that by polymerizing a photopolymerization initiator that absorbs visible light, it is possible to achieve even higher sensitivity, and to obtain a homogeneous resin, The present invention was devised based on the belief that a single phenomenon could be expected.

That is, the present invention provides a photosensitizing constitutive type i;t [A] consisting of a dialkylaminophenyl group represented by the general formula (Il) and rhodanine,
Structural unit ft represented by the general formula (Kawafu (in the formula, R3 represents at least one residue selected from a haalkyl group, a phenyl group, a vinyl group, an isopropenyl group, and a 2-alkylvinyl group)
31, and the general formula (wherein R4 represents a hydrogen atom or a methyl group, R5 represents a phenyl group, an alkoxycarbonyl group,
It is characterized by consisting of a vinyl 41 component unit (C) selected from a carbamoyl group, a 2-ketopyrrolidyl group, a cyano group, an alkoxy group, and an acyloxy group (all of which represent one type of residue). The present invention provides a photosensitized polymer having a molecular weight in the range of 1,000 to 1,000,000 in which structural units (5), (Bl, and (C1) are each 1 to 30.0 to 70.99 to O mol%, and a method for producing the same. be.

The present inventors have discovered that the residue having a rhodanine derivative represented by the general formula +11 used in the present invention becomes an efficient photopolymerization initiator for visible light. That is, by combining this rhodanine derivative with an auxiliary substance having electron-accepting ability, polymerization is initiated by visible light absorbed by this rhodanine derivative. According to the present invention, by bonding a photosensitive compound 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 polymerization. Sensitization is achieved.

In order to produce the polymer sensitizer of the present invention having these features, it is necessary to efficiently polymerize this relatively large molecular weight residue. The present invention also provides such a method. Below, a method for producing a photosensitizing polymer having a photosensitizing structural unit represented by general formula (1) will be explained.

In order to obtain the photosensitized polymer of the present invention, a polymer of chloromethylstyrene or a copolymer thereof is added to the general formula 1 (wherein R, R1, R2, and n have the same meanings as above,
A rhodanine derivative conjugated with a dialkylaminophenyl group represented by (M represents an alkali metal ion or a tetraargylammonium ion) may be reacted. Furthermore, if desired, a carboxylic acid salt represented by the general formula (V) MOCOR3... (■ (where M and lh have the same meanings as above) may be reacted.

In particular, by reacting the carboxylate represented by the general formula M, the physical properties of the resulting photosensitized polymer can be adjusted, and the storage stability of the polymer can be significantly improved by consuming the active and lolomethyl groups. can be increased. Alternatively, if an unsaturated carboxylic acid salt is used, since it will itself participate in photopolymerization, a highly sensitive photo-year-soluble resin composition can be provided.

Examples of rhodanine derivatives represented by the general formula (V) used here include salts of alkali metals such as lithium, sodium, and potassium of the following compounds, tetramethylammonium, tetraethylammonium, triethylbenzylammonium, etc. S Which ammonium ion can be mentioned.

-5 In addition, as the carboxylic acid salt represented by the general formula (■),
Acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, 2-
Ethylhexanoic acid, heptanoic acid, octane, alkyl carboxylic acids such as nonanoic acid and decanoic acid, acrylic acid, methacrylic acid, crotonic acid, α-methylcrotonic acid,
Suitable are unsaturated carboxylic acids such as 2-hexenoic acid, alkali metal salts such as lithium, sodium chloride, and potassium such as benzoic acid, and ammonium salts such as tetramethylammonium, tetramethylammonium, and triethylbenzylammonium.

As the muhinyl polymerization polymer containing at least 1 mol% of chloromethylstyrene used in the method for producing a photosensitized polymer in the present invention, a polymer of chloromethylstyrene or a copolymer thereof is preferable.

Comonomers in the copolymer include acrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. , ethyl methacrylate, methacrylic (392-, :c
f-/L/ H-t-shi/l/・N, N-dimethylacrylamide, N, N-dimethylmethacrylamide,
Examples include N-vinylpyrrolidone and styrene. these! It goes without saying that one or more l'-11 bodies can be used.

In order to react the rhodanine derivative represented by general formula 1 (1) and the carboxylic acid salt represented by general formula (2) with a chloromethylstyrene polymer or copolymer, it is preferable to carry out the reaction in a polar solvent.) .

Preferred polar solvents include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and dichlorobenzene.

The reaction temperature is preferably between room temperature and 120"C. If it is lower than this, the reaction time will increase significantly, and if it is higher than this, gelation may occur during the reaction. The reaction time depends on the reaction temperature and Although it depends on the reactivity of the polymer containing nitrogen, it takes about 1 to 20 hours.

Furthermore, in this method, an alkali salt of a compound represented by the general formula tn+ may be reacted with a halogen-containing polymer compound in an organic solvent using a crown ether, or an organic ammonium salt, a phosphonium salt, etc. (The reaction may be carried out in a two-phase system with an organic solvent using a multi-active catalyst.

Since the compound represented by the general formula A) has an amino group, there is a possibility that quaternization may occur due to the active chlorine group, but in reality, this amino group has a reduced reactivity due to the conjugated ketone via the benzene ring. Therefore, quaternization is unlikely to occur.

In order to prevent the product from gelling due to quaternization, the sum of the compounds represented by general formulas a to m and general formula M should be equal to -5 times the molar amount relative to the chloromethyl group. Just prepare it so that it becomes.

In the present invention, polymers having photosensitizing residues in their side chains, such as 71), cannot be made insolubilized by light irradiation alone, but compounds that transfer one electron and generate radical species upon light irradiation, ! (By allowing it to exist, it becomes a highly efficient photopolymerization initiation system. The one-electron one-element compounds used for this purpose are electron-accepting, and examples thereof include benzophenone, benzoquinone, naphthoquinone, T71-
Ketones or quinone compounds such as laquinone, benzanthrone, and fluorenone, iodonium-11 salts such as diphenyliodonium salts, ditolyliodonium salts, and di(Tn-nitrophenyl)iodonium salts, 2゜4
．． 6-) lis(trichloromethyl)-5-) riazine,
2-Methyl-4,6-bis(trichloromethyl)-3-
) riazine, S-trilyzine derivatives such as 2-phenyl-4°6-bis(trichloromethyl)-3-1 lyazine, P-nitrod.

σ, α-tribromoacetophenone, 0-nitroα,
d, α-tribromoacetophenone, σ.

σ, α ~ Trihaloacetylated benzene derivatives such as tribromoacetophenone, tribromomethanesulfonylbenzene, benzene derivatives having a trihalomethanesulfonyl group such as 1-)dibromomethanestronyl-3-nitrobenzene, and Among them, iodonium salts and triazine derivatives are effective.

These electron-accepting biocompounds can be made highly effective by mixing 0.5 to 10 mol, more preferably 1 to 5 mol, of the photosensitive residue represented by the general formula (I). It becomes a photopolymerization initiation system.

A light-year-soluble fat collapsing agent characterized in that it contains the polymer sensitizer of the present invention (1) [at least one ethylenically unsaturated bond having polymerization ability as a third component constituting the substitute] rll, α [Naruto C contains oligomers in the vinyl monomer pond, and may also be a high molecular weight compound.1
Physically, acrylic 1, methacrylic acid, crotonic acid,
There are high +'ji 1-point monomers such as itaconic acid, maleic acid, acrylamide, methacrylamide, diacetone acrylamide, ↑-vinylcarbazole, and also ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ], 3-
Propanediol, 1,4-butanediol, 1゜5-
Bentanediol, 1.6-hexylenediol, 1.
Di- or polyacrylic esters such as 10-decanediol, trimethylolethane, pentaerythritol, sorbitol, mannitol, di- or polymethacrylic esters, acrylated or methacrylated epoxy resins, polyester acrylate oligomers, acrylated or , methacrylated urethane oligomer, acroleinated polyvinyl alcohol, and the like.

The amount of these polymerizable compounds is preferably 0.1 to 5 parts per 1 part of the polymer sensitizer of the present invention. Moreover, it goes without saying that these polymerizable compounds need not be used alone and may be a mixture of two or more.

The photosensitive resin composition comprising the polymer sensitizer of the present invention becomes insolubilized at a very high rate with respect to light having a wavelength that is absorbed by the photosensitive group represented by the general formula (II). This is because this photosensitive group absorbs light energy and transfers electrons to the electron-accepting compound, and from the resulting cation radical represented by the following partial structural formula, 3 protons are removed from the alkyl group (R3). The generated radicals start polymerization and graft! This is thought to be due to R-coupling. 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 comprising the polymer sensitizer of the present invention exhibits high sensitivity.

Light sources suitable for the polymer sensitizer of the present invention include high-pressure mercury lamps, ultra-high-pressure mercury lamps, high-pressure xenon lamps, halogen lamps,
In addition to fluorescent lamps, H,e-Ca lasers and Ar lasers can be used.

The light-year-soluble resin composition comprising the polymer sensitizer of the present invention has superior characteristics in terms of sensitivity and resolution than conventional photopolymerizable compositions, so it can be used to create plate-making material relief for lithographic or letterpress printing. It can be applied to a wide range of fields, including the creation of non-silver halide images and the creation of printed wiring boards, and is also effective for negative plate making because it is sensitive to laser light. Furthermore, it can be used as an element material for photoelectric conversion.

Below, the present invention will be explained in more detail with reference to Examples.

Examples 1 and 2 4-oxo-5-
(p-diethylaminobenzylidene)thiazolidine-2
- 5 g of thione was added and stirred with gradual heating until the crystals were dissolved. Next, the solvent was distilled off from this solution under reduced pressure, and the precipitated crystals were recrystallized from ethanol to obtain a potassium salt.

Copolymer consisting of 53.8 g of methyl methacrylate and 6.2 g of chloromethylstyrene (mixture of meta and para isomers) (Mw = 6.15 x 10', Mn = 1
．． 82 x 105) 1,63 g was dissolved in 25 g of dimethylformamide, and 0.38 g of the above potassium salt was added to the solution while stirring at 75°C, and the mixture was reacted for 2 hours. The reaction solution was mixed with methanol-water (3:2) 2001
rLt to obtain a reddish-orange polymer into which a sensitizing group had been introduced. Dissolve this polymer in tetrahydrofuran,
When it was spin-coated onto a slide glass plate and its absorption spectrum was measured, it showed an absorption maximum value at 48] nm.

In the above reaction, a polymer into which a sensitizing group was introduced was obtained in exactly the same manner by using a p-dimethylaminobenzylidene derivative instead of a p-diethylaminobenzylidene derivative.

2 g of a 10% by weight solution of these polymers in tetrahydrofuran, 0.15 g of pentaerythritol triacrylate)
A photosensitive solution consisting of 36 m9 of diphenyliodonium hexafluorophosphate and 0.5 g of dichloroform was applied to an anodized aluminum plate, masked with Kodak Step Tablet Na 1, and exposed to a xenon lamp, resulting in 5 steps in 20 seconds each. It became insolubilized. This corresponded to about 10 times the sensitivity of the sensitized polyvinyl cinnamate-based photosensitive material.

Example 3 26.5 g of 3-(carboxymethyl)-4-oxo-5-(p-diethylaminobenzylidene)thiazolidine-2-thione was dissolved in 200 g of ethanol, and 5.0 g of potassium hydroxide (85%) was dissolved therein. Add 100ml of the dissolved ethanol solution, filter out the precipitate, and dry.
Potassium salt was obtained.

1.63 g of the methyl methacrylate-chloromethylstyrene copolymer used in Example 1 was dissolved in dimethylformamide 2
0.43 g of the above potassium salt was added to the solution while stirring at a liquid temperature of 75°C, and the mixture was reacted for 3 hours. The reaction solution was poured into a mixture of methanol and water (3:2) to sterilize the polymer. A film obtained by dissolving this polymer in tetrahydrofuran and spin coating showed an absorption maximum at 481 nm.

As a result of measuring the sensitivity in the same manner as in Examples 1 and 2, this polymer exhibited a sensitivity approximately 10 times that of the sensitized polyhinyl cinnamate.

Examples 4 to 10 1.26 g of a 1=1 copolymer of chloromethylstyrene and methyl methacrylate (N = 200,000) was dissolved in 20 g of dimethylformamide, and 0.53 g of potassium methacrylate was added while stirring at 75°C. In addition, the reaction was continued for 2 hours. Next, 0.34 g of the potassium salt used in Examples 1 and 2
The mixture was added and reacted at the same temperature for 2 hours. The reaction tube was spun down using a centrifuge, and the supernatant liquid was separated by decantation.
L. This was poured into a methanol-water mixed solvent to separate the polymer. This polymer was dissolved in tetrahydrofuran, diphenyliodonium hexafluorophosphate was added in an amount of 10% by weight based on the IJmer, and the solution was spin coated on anodized aluminum IN to measure sensitivity. A xenon lamp was used as a light source, and relative values were determined for polyvinyl cinnamate type photosensitive material, fJ (Tokyo Ohka Kogyo: TPR). Table 1 also shows the results of synthesizing polymers in exactly the same manner using various unsaturated carboxylic acids instead of potassium methacrylate and measuring their sensitivities. Light irradiation was performed not only in air, but also partially under vacuum degassing.

Claims (2)

[Claims] (1) A photosensitizing jf& component (5) consisting of rhodanine conjugated with a dialkylaminophenyl group represented by the general formula; - a structural unit FB represented by at least one residue selected from alkylvinyl groups)
+ and the general formula % formula % (wherein R4 represents a hydrogen atom or a methyl group, R5 haphenyl group, alkoxycarbonylnor, force/I/ hamoyl group, 2-ketopyrrolidyl group, cyano group, alkoxy group, acyloxy group The hexagram is composed of a vinyl 41η component (c) represented by a small number (each represents one type of residue), and each component is composed of (A), FB+, (c) casoresole 1 to 30. A photosensitized polymer having a molecular weight of 0 to 70.99 to 0 mol % in the range 1000-10000000)i'Q. (2) The 41"j structure consisting of 1 to 100 mol% of chloromethylstyrene represented by the general formula (11) and the general formula (% formula%) (wherein, R4 represents a hydrogen atom or a methyl group, and R5 represents a phenyl group, alkoxycarbonyl group, carbamoyl group, 2-ketopyrrolidyl method, cyano group, Al, poxy group,
acyloxino, a vinyl polymer consisting of 99 to 0 mol% of vinyl constituent units represented by a small number (both represent one type of residue) selected from () is conjugated with a dialkylaminophenyl group represented by the general formula A method for producing a patented polymer compound, which is characterized by reacting with rhodanine TS Md.