JPS6116389B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polymerizable heterocyclic compound useful for producing photoinsoluble polymeric substances and a method for producing the same. Recently, as the applications of photosensitive polymer materials have expanded, high sensitivity has been required. In general, photosensitive materials are those in which a crosslinking reaction occurs between polymeric compounds upon light irradiation, resulting in insolubilization of the exposed areas. There are two methods: a method of chemically bonding a photosensitive group to a polymer compound, and a method of polymerizing a monomer having a photosensitive group (see Ken Nagamatsu, "Photosensitive Polymer", Kodansha Scientific (1977)). . Many examples of each method have been reported. A highly sensitive photosensitive material is required to undergo a crosslinking reaction easily with a small amount of light, and to have as many photosensitive groups as possible in the material. From this point of view, the present inventor introduced a photosensitive group with excellent crosslinkability into the structure of a polymer compound, and
As a result of research aimed at developing highly uniform photosensitive materials, we have obtained a photosensitive group-containing polymerizable monomer that can be chemically introduced into polymeric compounds to provide excellent photosensitive materials. Successful. This monomer is
It is practically useful because it is uniformly distributed in the polymer compound, and the amount introduced can be lower than the conventionally known introduction rate, providing a highly sensitive material. Conventionally, vinyl monomers to which chalcone residues or cinnamic acid residues are bonded are known as photosensitive residue-containing monomers to be introduced into such polymeric compounds. However, these photosensitive groups have double bonds,
For example, when polymerizing by radical polymerization, gelation tends to occur due to the double bonds, and attempts have been made to reduce the degree of polymerization to prevent this, or to avoid such disadvantages by ionic polymerization. . As a method for preventing gelation in such a polymerization reaction, the present inventor copolymerized a photosensitive group-containing vinyl monomer with another monomer having vinyl polymerization ability, and used the former monomer. As a result of producing and studying various compounds containing photosensitive groups, which can suppress gelation by reducing the amount introduced, and which can be put to practical use at a low introduction rate, the present invention has been achieved. That is, the present invention provides the general formula (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a divalent organic residue, R ₃ is a hydrogen atom or an alkoxy group, Ar is a pyridyl, quinoline, or benzthiazolyl group, and n is a number of 0 or 1. A novel polymerizable heterocyclic compound containing a heterocycle conjugated with a double bond represented by (In the formula, R ₂ , R ₃ , n, and Ar have the same meanings as above) A method for producing a compound of the above general formula () is provided, in which a compound represented by the following is reacted with an acryloyl halide or a methacryloyl halide. It is something to do. As is clear from the above general formula (), the compound of the present invention has a structure in which an acryloyl or methacryloyl group and a styryl-substituted nitrogen-containing heterocycle are bonded, and the acryloyl or methacryloyl group in the compound participates in vinyl polymerization. It can be freely copolymerized with a wide range of other vinyl monomers. In the compound of the present invention, the nitrogen-containing aromatic heterocycle containing Z in the formula that is bonded to the styryl group is, for example,

【formula】 【formula】

[Formula] can be mentioned. These rings may be nuclear-substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. In addition, in the compound of the present invention, -O(-R ₂ ) _-o , which connects the acryloyl or methacryloyl group and the styryl nitrogen-containing heterocycle, is a divalent residue in addition to -O- when n=0. , for example -O- _CH2
−, −OCH ₂ CH ₂ O−, −OCH ₂ CH ₂ CH ₂ O−,

[Formula] etc., but any other divalent organic residue may be used as long as it can provide a photosensitive material that meets the purpose of the present invention. The compound represented by the general formula () of the present invention is
It can be easily obtained by subjecting the compound represented by the above general formula () to an acylation reaction with a halide or acid anhydride of acrylic acid or methacrylic acid. Examples of the compound represented by the general formula () used in such an acylation reaction include, but are not limited to, the following. Among the above compounds, for example, those of (1) to (8) are
WALees & A. Burawoy, Tetrahedron, 19 volumes,
It can be produced by dehydration condensation of the corresponding oxybenzaldehyde and a nitrogen-containing heterocycle having a methyl group according to the method described on page 419 (1963), and (9) and (10) The compounds are the corresponding compounds with phenolic hydroxyl groups ((9), (7),
(11)), WWCarlson & L.H.Cretsher, J.Am.
It can be produced by oxyethylation according to the method described in Chem.Soc., 69, 1952 (1947). Acryloylation or methacryloylation of the compound represented by the general formula () can be easily carried out by a commonly known method. Since the compound of the present invention has an acryloyl or methacryloyl group as the moiety involved in the vinyl polymerization reaction, the compound of the present invention is a derivative of acrylic acid or methacrylic acid,
For example, methyl acrylate, ethyl acrylate, butyl acrylate, acrylamide, N,N-dimethylacrylamide, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, dimethacrylate ,2,2-
It has excellent copolymerization ability with trifluoroethyl, benzyl methacrylate, methacrylamide, acrylonitrile, methacrylonitrile, etc., and also with vinyl monomers that can be copolymerized with these.
When the compounds of the present invention are copolymerized with those polymerizable vinyl monomers, the distribution of the compounds in the copolymer is uniform, and therefore the distribution of photosensitive groups is also uniform, and the resulting polymer It can give compounds excellent photosensitivity. The polymer compound obtained by introducing the compound of the present invention is photoinsolubilized with extremely high efficiency even if the monomer constitutional unit represented by the general formula () is extremely low, and provides a highly sensitive photosensitive material. . This is because the styryl-substituted heterocyclic photosensitive group in general formula () is not directly attached to the main chain of the vinyl copolymer, but is CO-O
This is presumed to be due to the relatively free movement of the photosensitive group in the polymer matrix because of the presence of two or more atoms called "-". As described above, the compounds of the present invention are extremely effective for producing photosensitive polymer materials that can be suitably used for, for example, printing plates, photoresist materials, ink vehicles, paint base materials, and the like. Next, the present invention will be explained in more detail with reference to Examples. Example 1 20.0 g of γ-picoline and 26.2 g of p-hydroxybenzaldehyde were heated under reflux for 24 hours in 65.8 g of acetic anhydride. 100 cm ³ of 6N hydrochloric acid was added to the reaction mixture, which was further refluxed for 60 minutes and then cooled. Aqueous ammonia was added to the reaction solution to neutralize it, and stirring was continued for 1 hour, and the precipitated yellow crystals were separated. The obtained crystals were recrystallized from an ethanol-ether mixture, and 35 g of 4-[2-(4-hydroxyphenyl)
Ethenyl]pyridine was obtained. The mp of this crystal is 272
It was ~275℃. Dissolve 2 g of this crystal in 10 cm ³ of dimethylacetamide and add triethylamine.
After adding 1.23 g, 1.34 g of methacrylic acid chloride was added dropwise while cooling with ice. After the reaction was completed, water was added to precipitate crystals. I collected this after passing through it. This was recrystallized with a mixed solvent of ethyl acetate and hexane, and the purified 4-[2-
(4-methacroyloxyphenyl)ethenyl]
2.16 g (yield 80%) of pyridine was obtained. The chemical structure was confirmed by infrared absorption spectrum and elemental analysis. Example 2 33.35 g of 4-methylquinoline and 29.88 g of p-hydroxybenzaldehyde were reacted in 71.36 g of acetic anhydride under reflux overnight. After about 50 cm ³ of acetic acid was distilled off, the reaction mixture was diluted with methanol and made alkaline by dropwise addition of an aqueous potassium hydroxide solution. After standing for 5 hours, the reaction mixture was neutralized with acetic acid and the crystals were separated. 41.84 g (yield 72.6%) of 4-[2-(4-hydroxyphenyl)ethenyl]pyridine was obtained. The crystals were purified by recrystallization using butyl cellosolve. After 5.10 g of purified crystals and 2.50 g of triethylamine were dissolved in 23 cm ³ of dimethylacetamide, 2.37 g of methacrylic acid chloride was added dropwise under ice cooling.
After the reaction was completed, the crystals obtained separately were recrystallized from a mixed solvent of ethyl acetate and hexane, and the mp130~
4-[2-(4-methacroyloxyphenyl)ethenyl]quinoline at 133°C was obtained. Its structure was confirmed from infrared absorption spectra and elemental analysis values. Example 3 In the same manner as in Example 2, 4-methylquinoline
The crystalline product obtained using 26.73 g of vanillin, 31.25 g of vanillin, and 62.9 g of acetic anhydride was recrystallized using butyl cellosolve to obtain purified 4-[2-(4- 29 g of hydroxy-3-methoxyphenyl)ethenylquinoline were obtained.
0.55g of this crystal mixture, 1.75g of triethylamine,
From 1.66 g of methacrylic acid chloride and 16 cm ³ of dimethylacetamide, 4-[2-(4
4.70 g (yield: 80.3%) of -methacryloyloxy-3-methoxy)ethenyl]quinoline was obtained.
This was recrystallized from ethyl acetate, and the above structure was confirmed by infrared absorption spectrum and elemental analysis. Example 4 In the same manner as in Example 2, 2-[2-(3-methoxy-4-hydroxyphenyl ) ethenyl]benzothiazole was obtained. This crystalline compound was methacryloylated in the same manner as in Example 2, and the yield was 80%.
[2-(3-methoxy-4-methacryloyloxy)ethenyl]benzothiazole was obtained. This structure was confirmed and determined by infrared absorption spectroscopy and elemental analysis. Example 5 4-[2-(4-hydroxy-3
-methoxyphenyl)ethenyl]quinoline 12.7g
and 38.3g of ethylene carbonate and dimethylacetamide
Dissolve in 50 cm ³ and add anhydrous potassium carbonate to this.
14.7g was added, heated to a temperature of 90-95°C, and reacted for 5 hours. After cooling, water was added to precipitate crystals, which were collected by filtration. By recrystallizing the obtained crystals using ethanol, mp178~
Purified crystal 4-{2-[3-methoxy-4-
(2-hydroxyethyl)phenyl)ethenyl}
Quinoline was obtained with a yield of 87%. Dissolve 1 g of this compound and 346 mg of triethylamine in 20 cm ³ of dimethylacetamide, then dissolve 390 mg of methacrylic acid chloride.
mg was added and reacted. After the reaction is complete, add water and
The precipitated crystals were collected by filtration and purified by silica gel chromatography. mp110~111℃
4-{2-[3-methoxy-4-(2-methacryloyloxyethyl)phenyl]ethenyl}quinoline was obtained in a yield of 55%. This structure was confirmed and identified by infrared absorption spectroscopy and elemental analysis.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a divalent organic residue, R ₃ is a hydrogen atom or an alkoxy group, Ar is a pyridyl, quinoline, or benzthiazolyl group, and n is a number of 0 or 1. ) A novel polymerizable heterocyclic compound containing a heterocycle conjugated with a double bond represented by: 2 General formula (In the formula, R ₂ is a divalent organic residue, R ₃ is a hydrogen atom or an alkoxy group, Ar is a pyridyl, quinoline, or benzthiazolyl group, and n is a number of 0 or 1) General formula characterized by reaction with acryloyl halide or methacryloyl halide (In the formula, R ₁ represents a hydrogen atom or a methyl group,
R ₂ , R ₃ , Ar, and n have the same meanings as above) A method for producing a polymerizable heterocyclic compound containing a heterocycle conjugated with a double bond represented by: