JP2627714B2 - Photosensitive resin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-resistant photosensitive resin, and more particularly, to a heat-resistant photosensitive resin having excellent mechanical properties and good solubility in organic solvents. And its manufacturing method.

[0002]

2. Description of the Related Art Photosensitive resins are highly useful materials used in various fields, such as resist materials, printing inks, paints, plate making materials, and adhesives. Generally, rubber, acrylic, acrylate, thiol, epoxy,
Silicone materials are widely or individually mixed
It is used. In particular, a photosensitive resin material using a sulfonyl azide compound and a rubber-based material having a double bond in a polymer molecular chain such as polyisoprene or polybutadiene,
A detailed study is reported in "Photoresist (1975)" by William S. Deforest, and it is known that the photoresist is a positive type photoresist that is insolubilized by a photoreaction by ultraviolet irradiation. Further, 1,2-polybutadiene having a double bond at a terminal or in a side chain shows ultraviolet light sensitivity in the presence of oxygen or in the presence of 4,4'-diazidophenyl, and becomes insoluble. Doing things, etc. (Preprints of the 32nd Annual Meeting of the Chemical Society of Japan, Spring Annual Meeting, 906 (1975))
Has been reported by

[0003] Further, as a photosensitive elastomer composition having another unsaturated double bond in a polymer structure, an elastomeric block copolymer obtained by anionic polymerization is known. For example, a solvent-soluble thermoplastic elastomer composed of a non-elastomeric polymer block having a glass transition temperature of 25 ° C. or higher and an elastomeric block having a glass transition temperature of 10 ° C. or lower, which is disclosed in JP-B-51-43374, Linear block copolymers are known. JP-B-63-70242 discloses a solvent-soluble thermoplastic multi-branched block copolymer in which a non-elastomer portion composed of a polyfunctional vinyl derivative and an elastomer portion composed of butadiene and isoprene derivatives are formed. ing. As another polymer material, polyvinyl cinnamate (US Pat. 2725372, JP-B-38) which is a polyvinyl-based material having no unsaturated double bond in the main chain.
-1492, Japanese Patent Publication No. 40-20188), cinnamic acid ester of ethylene-vinyl alcohol copolymer (US Pat. No. 3257664), cinnamic acid ester of glyptal resin (Koka, 68, 387 (196)
5)), cinnamic acid ester of epoxy resin (Brit.
Pat. 3257664), cinnamic acid esters of polyethers (JP-B-48-17000, JP-B-51-174)
65), a cinnamoyl-type polymer having a polystyrene skeleton (JP-B-49-46396), an acryl-type cinnamoyl-type polymer (JP-A-48-74594) and the like are well known. Is coming.

[0004]

However, the above-mentioned photosensitive resin compositions which have been proposed in the prior art have a temperature of from 10 to room temperature.
The target temperature range is around 0 ° C. In the higher temperature range, it is easily deformed thermally, and it is thermoplastic and has a double bond at the end. Consideration at the time of processing was necessary, for example, a thermal polymerization inhibitor had to be added. The present invention has been made in view of the above-described problems in the related art. Therefore,
An object of the present invention is to provide a photocurable resin that can be used in a high temperature range (150 ° C. or higher).

[0005]

Means for Solving the Problems The present inventors have conducted research to solve the above-mentioned problems in the prior art, and as a result, in order to impart heat resistance to a photosensitive resin, a photosensitive group was added. Instead of polyvinyl alcohol, which can be easily introduced,
By focusing on the aromatic polyamide having a reactive group capable of introducing a photosensitive group, the inventors have found that the above problems can be solved, and have completed the present invention.

The present invention has a structure represented by the following general formula (I) and has a weight average molecular weight in terms of polystyrene of 2,000.
Photosensitive resin having a range of 400,000.

Embedded image Wherein R is an aromatic group, and Ar is a phenylene group or

Embedded image In one formula, X is _{-CO -, - SO 2 -,} - S -, - CON
H -, - O -, - Si (CH 3) 2 -O -Si (CH 3) 2 -, showing a)
Wherein Z is a divalent aromatic group represented by the following formula:

Embedded image -CO-CH = CH-R 'or -CH ₂ -C
H = CH-R '(wherein, R' represents an aliphatic group having 10 or less carbon atoms, a cyclic aliphatic group or an aromatic group), and l and m are photosensitive groups. Indicates the introduction ratio of the group Z, and 1 / (l
+ M) is a ratio of 0.01 to 1.0, and n indicates the degree of polymerization)].

The photosensitive resin represented by the general formula (I) comprises an aromatic polyamide having a phenolic hydroxyl group represented by the following general formula (II) and the following general formula (III) or (I)
It can be produced by reacting the compound represented by V) in the presence of a polar solvent.

Embedded image (Wherein, R, Ar, and n are as defined above)

Embedded image Y—CO—CH ＝ CH—R (III) (wherein Y represents a halogen atom, and R ′ has the same meaning as described above.)

Embedded image Y—CH ₂ —CH ＝ CH—R (IV) (wherein Y and R ′ are as defined above)

The aromatic polyamide having a phenolic hydroxyl group as a reactive group represented by the general formula (II) used in the present invention may be synthesized by any method. The presence of a phosphite ester catalyst in an amide-based organic solvent represented by N-methyl-2-pyrrolidone, comprising an aromatic diamine compound represented by the formula and an aromatic dicarboxylic acid having a phenolic hydroxyl group represented by the general formula (VI): It can be synthesized by polycondensation under heating and heating.

Embedded image (Wherein, R, Ar, and n are as defined above)

As the aromatic diamine represented by the above general formula (V), for example, metaphenylenediamine, paraphenylenediamine, 4,4'-ethylenedianiline,
4'-isopropylidene dianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 3,3'-
Sulfonyl dianiline, 4,4'-sulfonyl dianiline, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 1,3-bis (methaminophenyl) -1,1,3 , 3-tetramethyldisiloxane, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis (3-aminophenoxy) diphenylsulfone, 4,4'-bis (4
-Aminophenoxy) benzophenone, 4,4'-bis (3-aminophenoxy) benzophenone, 4,4'-
Bis (4-aminophenylmercapto) benzophenone, 4,4'-bis (4-aminophenylmercapto)
Benzophenone, 2,2'-bis (4- (2-trifluoromethyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (3-trifluoromethyl-5-aminophenoxy) Phenyl) hexafluoropropane, 2,2'-bis (4- (3-trifluoromethyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-5 -Aminophenoxy) phenyl)
Phenyl) hexafluoropropane, 2,2'-bis (4- (4-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (2-nonafluorobutyl-5 -Aminophenoxy) phenyl) hexafluoropropane, 2,2'-
Bis (4- (4-nonafluorobutyl-5-aminophenoxy) phenyl) hexafluoropropane, 4,4 '
-Diaminophenylmethane, o-tolidine, o-dianisidine, and the like, but are not limited thereto. These aromatic diamines may be used alone or in combination.

The dicarboxylic acids represented by the general formula (VI) include 2,5-dihydroxy-1,4-benzenediacetic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, and 4,6-dihydroxyisophthalic acid. And the like, and their derivatives, but are not limited thereto. These may be used alone or in combination of two or more. Examples of the phosphite used in this synthesis include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, and tri-m-tolyl phosphite. Di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-phosphite -P-chlorophenyl and the like, but are not limited thereto. Furthermore, pyridine, 2-picoline, 3-picoline, and 4-pyridine as the pyridine derivative used together with the phosphite in the present invention.
Picoline, 2,4-lutidine, 2,6-lutidine, 3,
5-lutidine and the like can be mentioned.

In the above reaction, polycondensation is carried out in the presence of a phosphite and a pyridine derivative. In this reaction, a solution polymerization method using a mixed solvent containing the pyridine derivative is usually employed. Here, the organic solvent used is limited in that it does not substantially react with both the reaction components and the phosphite, but in addition, it is a good solvent for both the reaction components and the reaction product A good solvent for the polymer is desirable. Representative examples of such organic solvents are amide solvents such as N-methyl-2-pyrrolidone and dimethylacetamide.
Here, in order to obtain a polymer having a high degree of polymerization, alkali metal salts represented by lithium chloride and alkaline earth metal salts represented by calcium chloride can be added to the reaction system.

The amount of the pyridine derivative used here is as follows:
It is necessary that the amount be at least equimolar to the carboxyl group, but in practice, it is often used in a large excess including its role as a reaction solvent. Here, the pyridine derivative and N-
A mixed solvent composed of an organic solvent represented by methyl-2-pyrrolidone is preferably used, but the amount of the mixed solvent used is usually an amount sufficient to contain 5 to 30% by weight of the reaction components. . The reaction temperature is usually 6
A range of 0-140 ° C is preferred. The reaction time is greatly affected by the reaction temperature, but in any case it is advisable to stir the reaction system until the highest viscosity, which means the highest degree of polymerization, is obtained, often between a few minutes and 20 hours.

Under the above reaction conditions, it is possible to produce a polymer having an average degree of polymerization of 2 to 20 using an equimolar amount of the reaction components. If the average degree of polymerization exceeds 20, it is not preferable in terms of processability and the like, but for a specific purpose, one of them can be excessively used to reduce the average degree of polymerization. After completion of the reaction, the reaction mixture is poured into a non-solvent such as methanol or hexane to separate the produced polymer, and further purified by a reprecipitation method to remove by-products, inorganic salts, and the like. Coalescence can be obtained. In this way, an organic solvent capable of favorably dissolving the aromatic polyamide with the compound represented by the general formulas (III) and (IV), which are photosensitive groups, using the obtained aromatic polyamide as a main raw material Among them, the photosensitive resin of the present invention can be synthesized by using a generally known method.

Further, in order to obtain a good cured photocurable resin, a photopolymerization initiator can be mixed and used. Specific examples include benzophenone, benzoin, alkyl ethers of benzoin such as methyl, ethyl, isopropyl and isobutyl ether of benzoyl, α-methylbenzoyl, α-methoxybenzoin methyl ether, α-methylbenzoin methyl ether, benzoin phenyl ether, α- t-butylbenzoin, anthraquinone, 2-chloroanthraquinone, 2,2'-dimethoxyphenylacetophenone, 2,2-diethoxyacetophenone, benzyl, bivaloin, 2,4,6-trinitroaniline, 1-nitropyrene, 1,8 -Dinitropyrene, cyanoacridine, azobisbutyronitrile, 2,2'-azobispropane, m, m'-azoxystyrene, benzoyl peroxide, di-tert.
Butyl peroxide, 1- or 2-naphthyl peroxide, diphenyl sulfide, diphenyl disulfide, dibenzyl sulfide, dibenzyl disulfide, dibenzothiazoyl disulfide, methyl diethyl dithiocarbamate, S-acyl dithiocarbamate,
Decylthiobenzoate, p, p'-tetramethyldiaminobenzophenone, N-acetyl-4-nitro-1-
Although naphthylamine etc. can be mentioned, it is not limited to these. The amount of the compound to be used is generally 0.01 to 5 parts by weight in the photosensitive composition, and one or two or more of the compounds can be used.

In addition to the above photopolymerization initiator, a photosensitization aid may be used for the purpose of broadening the photosensitization wavelength range. Examples of the auxiliary agent include quinone compounds such as 1,2-benzoanthraquinone and anthraquinone, 5-nitrofluorene,
Examples thereof include aromatic nitro compounds such as 5-nitroacenaphthene and ketone compounds other than the above, but are not limited thereto. Further, as a method used for obtaining a film-like molded product, a solvent casting method by a usual method of casting a solution of the photocurable resin composition on an appropriate substrate is desirable. Usually, the solution-type photocurable resin composition of the present invention is cast on a suitable substrate, dried by a conventional method,
By peeling off from the substrate, a film-shaped molded product is obtained.

As the molding substrate, it is desirable that a film-like molded product can be easily formed on the surface of the substrate and can be peeled off, and the material is not particularly limited. For example, a glass plate or a pet film having a smooth surface, a polymer film such as a Kapton film, an aluminum plate, a metal plate such as a copper plate, the above-mentioned material which has been subjected to a surface treatment with a metal net-shaped molded product or a release agent. Can be used without any problem. As a light source that can be used in the photocuring method of the photosensitive resin composition of the present invention, a light source such as an ultraviolet fluorescent lamp, a low-pressure mercury lamp, and a high-pressure mercury lamp can be used, and the irradiation time is several minutes to several hours. Distance to the
It is set by light source illuminance and photosensitivity. The photosensitive resin composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor, a coloring agent, a filler (inorganic powder, glass fiber, shirasu balloon, glass hollow body, etc.), and other chain transfer agents. In addition, it can be used.

[0017]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. Synthesis Example 1: Synthesis of aromatic polyamide having cinnamoyl group In a 100 ml three-necked round bottom flask, 1.820 g (10 mmol) of 5-hydroxyisophthalic acid, 2.002 g (10 mmol) of 3,4'-oxydianiline, chloride 1.01 g of calcium, 0.33 g of lithium chloride, 20 ml of N-methyl-2-pyrrolidone, 3 ml of pyridine and 6.20 g of triphenyl phosphite were added, and dried under a stream of nitrogen.
The polycondensation was performed at 00 ° C. for 3 hours. This was allowed to cool to room temperature, diluted with 40 ml of N, N-dimethylacetamide, and poured into an 800 ml methanol precipitation bath with stirring to obtain a polymer powder. This crude polymer was purified by a conventional method. 3.40 g (98% yield), intrinsic viscosity η inh = 0.35 dl / g (measured in N, N-dimethylacetamide with an Oswald viscometer at 30 ° C.), weight average molecular weight in terms of polystyrene of about 36,000
(GPC method, solvent 0.1 wt.% LiBr / N-methyl-2-pyrrolidone, column: Shodex KD-80
M). In order to introduce a cinnamoyl group, which is a photosensitive group, into the crude polymer, 2.0 g of the crude polymer was dissolved in 40 ml of pyridine, and then lithium chloride was added.
After adding and dissolving 0 g, 1.62 g of cinnamoyl chloride was added, and the mixture was stirred and reacted at room temperature for 24 hours. After the reaction,
The mixture was poured into 1 liter of methanol, and the crude photosensitive resin was purified by a conventional method to obtain 2.40 g of the desired product at a cinnamoyl group introduction rate of 75% (quantified by ¹ H-NMR method).

Synthesis Example 2: Synthesis of aromatic polyamide having a cinnamoyl group An aromatic polyamide having a phenolic hydroxyl group as a main raw material was synthesized in the same manner as in Synthesis Example 1 (yield 3.30 g, 97)
%), Intrinsic viscosity η inh = 0.45 dl / g (30 ° C.,
N, N-dimethylacetamide in Oswald viscometer), polystyrene equivalent weight average molecular weight of about 580
00 (GPC method, solvent 0.1 wt.% LiBr / N-methyl-2-pyrrolidone, column: Shodex KD-
80M) in a 100 ml three-necked round bottom flask, 3.0 g of the crude polymer was added to N, N-dimethyl-imidazolidinone 4
After dissolving in 0 ml, 0.2 g of metallic Na was added, and the mixture was stirred, 1.52 g of cinnamoyl chloride was added in 10 minutes, and the mixture was reacted at room temperature for 24 hours. After the reaction, the reaction solution was slowly dropped into 2 liters of methanol to precipitate a reaction product. After filtration, the resultant was purified by a conventional method to obtain a photosensitive polymer in a yield of 2.8 g.

Example 1 2.0 g of the photosensitive resin obtained in Synthesis Example 1 was dissolved in 8 ml of N, N-dimethylacetamide, and then dissolved in 20 cm × 2.
It was drooled on a glass substrate of 0 cm, and a cast film was prepared by a conventional method, and EYE GRANDAGE ESC-310 was prepared.
Type UV irradiation device (light source: metal halide lamp, light intensity:
(120 w / cm). Example 2 1 part by weight of Michler's ketone as a sensitizer was added to the coating material of Example 1 and evaluated similarly. Example 3 The sensitizer of Example 2 (1 part by weight of Michler's ketone) was added to 1,2
-The same evaluation was performed in place of 1 part by weight of benzanthraquinone. Example 4 The photosensitive resin obtained in Synthesis Example 2 was processed and evaluated in the same manner as in Example 1. Example 5 The photosensitive resin obtained in Synthesis Example 2 was processed and evaluated in the same manner as in Example 2. Example 6 The photosensitive resin obtained in Synthesis Example 2 was processed and evaluated in the same manner as in Example 3.

Evaluation Results Photosensitivity was evaluated by a solubility test of the sample films in N, N-dimethylformamide after a light irradiation time of 10 and 30 minutes. The results are shown in Table 1. The heat resistance was evaluated by thermogravimetry (TGA analysis: TG / DTA22 manufactured by Seiko Denshi Co., Ltd.).
0, a nitrogen atmosphere, and a heating rate of 10 ° C./min). As a result, at around 100 to 200 ° C., weight loss due to water and the organic solvent remaining in the sample film was observed. Thermal decomposition starts around 270 ° C (here, 100
%) And the 10% decrease temperature is 495.6 ° C.
It can be seen that the composition has good thermal stability.

[0021]

[Table 1]

[0022]

The photosensitive resin of the present invention has an aromatic polyamide main chain having excellent mechanical strength as compared with ordinary photosensitive resins, and has good solubility and thermal stability in amide organic solvents. And in fields requiring strength. By controlling the molecular weight of the aromatic polyamide as the main raw material and the amount of the photosensitive group introduced, a wide range of physical property control is possible, and wide application is expected.

Claims (2)

(57) [Claims] 1. It has a structure represented by the following general formula (I), and has a polystyrene equivalent weight average molecular weight of 2,000 to 40.
A photosensitive resin in the range of 0000; Embedded image [Wherein, R is an aromatic group, Ar is a phenylene group or the following formula: (Wherein, X is _{-CO -, - SO 2 -,} - S -, - CON
H -, - O -, - Si (CH 3) 2 -O -Si (CH 3) 2 -, showing a)
In a divalent aromatic group represented, Z is formula ## STR3 ## -CO-CH = CH-R 'or -CH ₂ -
CH = CH-R '(wherein, R' is an aliphatic group having 10 or less carbon atoms, a cyclic aliphatic group or an aromatic group), and l and m are photosensitive groups. Indicates the introduction ratio of the group Z, and 1 / (l
+ M) is a ratio of 0.01 to 1.0, and n indicates the degree of polymerization)]. 2. A method comprising reacting an aromatic polyamide having a phenolic hydroxyl group, which is a precursor represented by the following general formula (II), with a compound represented by the following general formula (III) or (IV): A method for producing a photosensitive resin represented by the general formula (I): Embedded image (Wherein R, Ar, and n have the same meanings as described above.) Y-CO-CH = CH-R (III) (wherein Y represents a halogen atom, and R 'represents the same as above.) Y—CH ₂ —CH ＝ CH—R (IV) (wherein Y and R ′ are as defined above)