JPH03186849A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the heat resistant photosensitive polyimide resin compsn. with which the production process is simple and which is free from the fluctuation in products, allows spray development and has a high sensitivity by incorporating a specific polymer, styryl compd. and oxazolone compd. which are respective specific into the compsn. CONSTITUTION:This compsn. consists essentially of the polymer (A) essentially consisting of the constitutional unit expressed by formula I, the styryl compd. (B) expressed by formula II and the oxazolone compd. (C) expressed by formula III and is compounded with 1 to 10pts.wt. (B) and 1 to 20pts.wt. (C) per 100pts. wt. (A). In the formulas I to III, R1, R2 denote an arom. cyclic group; R3 denote -H, -CH3, etc., R4 denotes -H, -CH3, etc.; n denotes 1 to 2; m denotes 0 to 2; R5 denotes -H, -CH3, etc.; R6 is formula IV, etc.; R7 is formula V, etc.; R8 is -H, -CH3, etc. The compsn. with which the production process is simple and which is free from the fluctuation in the products, allows the spray development and has the high photosensitivity is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive polyimide resin composition with high sensitivity and high heat resistance.

[Conventional technology] Conventionally, surface protective films and interlayer insulating films for semiconductor devices have been known to have heat resistance, excellent electrical properties, mechanical properties, etc. Polyimide resin is used, but
In recent years, as semiconductor devices have become more highly integrated and larger, sealing resin packages have become thinner and smaller, and there has been a shift to surface mounting methods with one flow of solder, the heat cycle resistance and thermal shock resistance of copper have increased. 1-, which has been difficult to meet with conventional polyimide resins.

On the other hand, technology that imparts photosensitivity to polyimide resin itself has recently attracted attention.

Using polyimide resins that have been added with these photosensitizers not only simplifies the pattern creation process compared to polyimide resins that have not been added with photosensitivity, but also eliminates the need to use highly toxic etching liquids. It is also superior in terms of safety and pollution, and photosensitization of polyimide resin is expected to become an important technology in the future.

As the photosensitive polyimide resin, for example, a polyimide precursor composition to which a photosensitive group is added with an ester group having a structure as shown in the following formula (CIV) specification (no change in content) (Japanese Patent Publication No. 55-414-22) is used. Alternatively, a compound containing a carbon-carbon double bond and an amino group that can be dimerized or polymerized by actinic radiation or a quaternized salt thereof is added to a polyamic acid having a structure as shown in the following formula (V). Compositions (for example, Japanese Patent Publication No. 59-52822) are known.

All of these are dissolved in a suitable organic solvent, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and then heat-treated to form a polyimide. It appears as a film.

However, such conventional compositions have the following drawbacks. That is, in the composition shown by formula (IV), the extremely complicated process of first esterifying a tetracarboxylic dianhydride and an alcohol having a photosensitive group and then performing an amidation reaction with a diamine is performed. This made it difficult to stabilize the product. In the composition shown by formula (V), the manufacturing process is extremely simple because it is only necessary to add and mix the photosensitizer to the polyamic acid, but the ionic bonding force between the polyamic acid and the photosensitizer is extremely weak.
Spray development (a method of rapidly developing in a short period of time by spraying a developing solution), which is possible with the composition shown in formula (TV), was not possible.

[Problems to be Solved by the Invention] An object of the present invention is to provide a highly sensitive heat-resistant photosensitive polyimide resin composition that has a simple manufacturing process, is consistent in product quality, can be spray developed, and is highly sensitive. There is something to do.

[Means to solve the problem] The present invention is based on the following general formula [I] R4R3 (In the formula R1゜ R3: R4: R2: aromatic cyclic group.

H, CH3, C2H5 H, CH3, C2H5°CH20H, C6H5 Copying of specification (no change in content) n: 1-2. ml-2) and a styryl compound el(B ) and the engraving of the following general specification (no change in content) Re: -H, -CR3, -C2H5, -C3H7,
-C4H9゜CaH2, -0I-I, -OCH3, -O
C2H5゜OC3H,, -OC4H,, -OC5H5
゜-ClT2C6115,-CH2CH2C6H5゜C
I (20H, -CI 2CI■20H.

-CH2CH3, -CTJ (CI 3)2. -C(C
H3) 3゜-COCl(s, -COC,d(5,-0C
OCH3゜-OCOC2H,, -c H2NH2゜-C
H2CH2N R3, -CON R2゜-CONHCI
(3,-CON(CH3)2゜-CONHC2H5,-
CON(C2H5)2゜-N HCH3,-N (CH
3)2. The oxacylone compound (C) represented by -N (C2H5)2) is an essential component, and (B) is 1 part by weight per 100 parts by weight of (A).
-10 parts by weight and (C) 1 to 20 parts by weight.

[Effect] Polymer (A) used in the present invention teeth, example It can be synthesized by the following method.

That is, the acid shown in the following format (Vl) (when n = 1) (when n = 2) [■] and the acid shown in the following format [■] (COOH)□ H2N R2 H2 [■] An amine and an N-methylolacrylamide represented by the following format [■] 0H2C\0, (V
It is synthesized by reacting T) and [■], then adding [■] and further reacting. (The reaction between VD and [■] is usually completed in several hours at room temperature, and the reaction with [■]
The process is completed in half an hour to several hours at 0 to 100°C. The reaction will complete more quickly if a catalyst is used, but it will proceed satisfactorily even without a catalyst. In this way, the reaction can be completed extremely easily and consistently.

In the general formula (Vl), as the acid having an aromatic cyclic group ft, tricarboxylic acid anhydride where n=1 or n=
Tetracarboxylic dianhydride of No. 2 is used, and the acid anhydride component may be one type or a mixture of two or more types. The types of acid anhydrides used include, for example, trimellitic anhydride, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3.3
', 4.4'-benzophenone tetracarboxylic dianhydride, 2.2', 3.3'-benzophenone tetracarboxylic dianhydride, 2,3.3'.

4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride,
Naphthalene-1,2,5,6-tetracarboxylic dianhydride, Naphthalene-1,,2,4,5-tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride Naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,,2,3,
5,6,7-hexahydronaphthalene-1,2,5,6
-tetracarboxylic dianhydride, 4,8 dimethyl-1,2
,3,5,6,7-hexahydronaphthalene-2, :I
, 6.7-tetracarboxylic dianhydride, 2,6-cyclonaphthalene-1. , 4, 5, 8-tetracarboxylic dianhydride, 2,7-cyclonaphthalene-1. ．． 4
, 5.8-tetracarboxylic dianhydride, 2,3,6.7
-Titrachloronaphthalene-1.4,5.8-tetracarboxylic dianhydride, ], 4,5°8-Tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3. 3',4.4'-diphenyltetracarboxylic dianhydride, 2.2',3.3'-diphenyltetracarboxylic dianhydride, 2,3.3',4'-diphenyltetracarboxylic dianhydride thing, 3.3", 4.4"-p-
Terphenyltetracarboxylic dianhydride, 2.2”, 3
．． 3”-P-terphenyltetracarboxylic dianhydride,
2,3゜3'',4''-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propanihydride, 2,2-bis(3,4- dicarboxyphenyl)-propanihydride, bis(2,
3-dicarboxyphenyl)ether dianhydride, bis(
3,4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride,
Bis(3,4-dicarboxyphenyl)methanihydride, bis(2,3-dicarboxyphenyl)sulfonic anhydride, bis(3,4-dicarboxyphenyl)sulfonic anhydride, 1, L-bis(2, 3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, perylene-2,3,8
, 9-tetracarboxylic dianhydride, perylene-3,4,
9,10-tetracarboxylic dianhydride, perylene-4,
5,1,0,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride,
Phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2゜9, lO-
Tetracarboxylic dianhydride, cyclopentane-13-1,2,3,4-te1helacarboxylic dianhydride, pyrazine-2゜3.5.6-tetracarboxylic dianhydride, pyrrolidine-2゜3.4.5-tetracarboxylic dianhydride,
Examples include, but are not limited to, thiophene-2°3.4.5-tetracarboxylic dianhydride.

- In the format [■], as the amine having an aromatic cyclic group for R2, m=00 diamine, m=1 diaminocarboxylic acid, m=2 diaminodicarboxylic acid, etc. are used, and even one type of amine component is used. , a mixture of two or more types may be used. Examples of the types of amines used include m
-phenylene-diamine, l-isopropyl-2,4-
Phenylene diamine, p-phenylene diamine, 4
, 4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diamino-diphenylethane, 3,3'-diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3, 3'
-diamino-diphenylmethane, 4,4'-diamino-
diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl 4-sulfone, 4,4'-diamino-diphenyl ether,
3,3'-diamino-diphenyl ether, benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4'diamino-biphenyl, 3,3'-dimethoxy-benzidine, 4,4''-diamino -p-terphenyl, 3.3″diamino-p-terphenyl, bis(p-terphenyl
-amino-cyclohexyl)methane, bis(p-β-amino-t-butylphenyl)ether, bis(p-β-
Methyl-δ-aminopentyl)benzene, p-bis(2
-Methyl-4-amino-pentyl)benzene, p-bis(1,1-dimethyl-5-amino-pentyl)benzene, 1,5-diamino-naphthalene, 2,6-cyamitunaphthalene, 2,4-bis (βamino-t-butyl)toluene, 2,4-diamino-toluene, m-xylene-
2,5-diamine, p-xylene-2゜5-diamine,
m-xylylene-diamine, p-xylylene-diamine, 2,6-cyamitopyridine, 2,5-diamino-pyridine, 2,5-diamino-], 3,4-oxadiazole, 1,4-diamino -cyclohexane, piperazine, methylene-diamine, ethylene-diamine,
Propylene-diamine, 2,2-dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine, hexamethylene-diamine, 2゜5-dimethyl-hexamethylene-diamine, 3-methoxy-hexamethylene-diamine, heptamethylene diamine, 2,
5-Dimethyl-heptamethylene-diamine, 3-methyl-heptamethylene-diamine, 4,4-dimethyl-heptamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methyl-nonamethylene-diamine, 2,5- dimethyl-nonamethylene-diamine,
decamethylene-diamine, 1,10-diamino-1,
10-dimethyl-decane, 2,11-diamino-dodecane, 1,12-diamino-octadecane, 2,12-diamino-octadecane, 2,17-diaminosiloxane,
Examples include, but are not limited to, diaminosiloxane, 2,6-diamino-4-carboxylic benzene, and 3,3'-diamino-4,4'-dicarboxylic benzidine.

- N-methylol acrylamides represented by the format [■] include N-methylol acrylamide, N-methylol methacrylamide, N, N-di Methylol methacrylamide, N-methylol-N-methylacrylamide, N-methylol-N-methylmethacrylamide,
Examples include, but are not limited to, N-methylol-N-ethyl acrylamide and N-methylol-N=ethyl methacrylamide.

The sensitizer of component (B) in the present invention has the following formula (in the formula R5
;-i(, -CH3, -C2H5, -C6H5.

7 Ru.

Sensitizers used in the photosensitive resin composition include benzophenone, acetophenone, anthrone, p,p'-tetramethyldiaminobenzophenone (Michler ketone),
Phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, N-acetyl-p-nitroaniline, p-di[・roaniline, 2-ethylanthraquinone, 2-tert-butylanthraquinone, N-
Acetyl-4-nitro-1-naphthylamine, picramide, 1,2-benzanthraquinone, 3-methyl-1,
3-Diaza-1,9-benzanthrone, p,ρ'-tetraethyldiaminobenzophenone, 2-chloro-4-
Nitroaniline, dibenzalacetone, 1,2-naphthoquinone, 2,5-bis=(4'-diethylaminobenzal)-cyclopentane, 2,6-bis-(4'-diethylaminobenzal)-cyclohexanone, 2 .6-bis-(4'-dimethylaminobenzal)-4-methyl-cyclohexanone, 2,6-bis-(4'-diethylaminobenzal)-4-methyl-cyclohexanone, 4.4
'-Bis-(dimethylamino)-chalcone, 4,4'-
Bi-18-su(diethylamino)-chalcone, p-dimethylaminobenzylideneindanone, 1,3-bis-(4'-dimethylaminobenzal)-acetone, 1,3-bis-(
Examples include 4'-diethylaminobenzal)-acetone, N-phenylene/L-jetanolamine, N-p-)-lyludiethylamine, and the styryl compound discovered in the present invention can be used as an initiator in the present invention. It shows a surprisingly excellent sensitizing effect only when used in combination with the oxacylone compound used. The reason for this surprising synergistic effect is not yet clear.

In addition, the blending amount of the styryl compound is polyamic acid 100
It is most preferably 1 part by weight or more and 10 parts by weight or less based on the weight part, and sensitizers other than styryl compounds may also be used in combination.

If the amount of the styryl compound is less than 1 part, the absorption of light energy will be insufficient and crosslinking will be insufficient.
If the amount exceeds 10 parts by weight, the amount of light energy transmitted is insufficient, and deep photocuring proceeds rapidly, which is not preferable.

The initiator of component (C) in the present invention is an oxacylone compound having a phenyl group represented by the following formula: %))))).

As an initiator used in the photosensitive resin composition, 2.2-
Dimethoxy-2-phenyl-acetophenone, 1-hydroxy-cyclohexyl-phenylketone, 2-methyl-14-(methylthio)phenyl]-2-morpholino-1-propane, 3.3', 4.4'-tetra −(t
-butylperoxycarbonyl)benzophenone, benzyl, benzoin-isopropyl ether, benzoin-isobutyl ether, 4,4'-dimethoxybenzyl, 1,4-dibenzoylbenzene, 4-benzoylbiphenyl, 2-benzoylnaphthalene, methyl-〇- Benzoylbenzoate, 2,2'-bis(0-chlorophenyl)-4,4', 5,5'-tetraphenyl-1,
2'-biimidazole, 10-butyl-2-chloroacridone, ethyl/l, -4-dimethylaminobenzoate, dibenzoylmethane, 2,4-diethylthioxanthone, 3,3-dimethyl-4-methoxy-benzophenone, 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-
Hydroxy-2-methylpro1 pan-1-one, 1-(4-dodecylphenyl)-2-
Hydroxy-2-methylpropan-1-one, 1-phenyl-], 2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-propanebutanedione-2-(O-benzoyl)oxime, 1, 2-diphenyl-ethanedione-1-(O-benzoyl)oxime, 1,3-siphenin l-propanetrione-2-(0
-benzoyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2-(Qbenzal) oxime, etc., but the oxacylone compound discovered in the present invention is a combination with styryl compound as a sensitizer. Depending on the combination, the photoreaction initiation effect was significantly greater than that of other initiators.

The reason for how this surprising effect is expressed is currently not clear.

The amount of the oxacylone compound to be blended is essentially 1 to 20 parts by weight per 100 parts by weight of the polyamic acid, and initiators other than the oxacylone compound may also be used in combination.

1 part by weight of an oxacylone compound as an initiator If it is less than that, the photosensitivity will not be sufficient, which is not preferable.

Moreover, if it exceeds 20 parts by weight, the film properties after heat treatment and curing will deteriorate.

An adhesion aid, a leveling agent, and various other fillers may be added to the heat-resistant, photosensitive resin composition of the present invention.

The method for using the photosensitive resin composition according to the present invention is to first apply the composition to a suitable support such as a silicon wafer or a ceramic substrate. Application methods include rotation application using a spinner, spray application using a spray coater,
This can be done by dipping, printing, roll coating, etc. next,
After drying the coating film by prebaking at a low temperature of 60 to 80°C, the desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible light, etc. can be used, but those having a wavelength of 200 to 500r+[11] are preferable.

Next, a relief pattern is obtained by dissolving and removing the unirradiated areas with a developer. As a developer, N-methyl-2
-pyrrolidone, N,N-dimethylacetamide, N,N
-Dimethylformamide, methanol, isopropyl alcohol, water, toluene, xylene, etc. are used alone or in combination. Development methods include spray,
Methods such as paddle, immersion, and ultrasonic waves are possible, among which development 11. Spray development is most preferable because it has the shortest time interval, can be incorporated in-line into the process, and has the most consistent finished pattern. In spray development, the developer is sprayed under considerable pressure, so unless the coating film has zero or extremely low solubility in the irradiated areas, it will dissolve together with the unirradiated areas, leaving no relief pattern. Put it away. Although many conventional compositions cannot be spray developed, the composition according to the present invention can be developed and can be directly incorporated into an in-line process.

Next, the relief pattern formed during development is rinsed. As a rinsing liquid, methanol, ethanol,
Use isopropyl alcohol, butyl acetate, etc.

Next, heat treatment is performed to form imide rings and obtain a final pattern with high heat resistance.

The photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as an interlayer insulating film for multilayer circuits, a cover coat for flexible copper clad boards, a solder resist film, a liquid crystal alignment film, and the like.

The present invention will be specifically explained below using Examples.

Example] 57 g of 3.3',4.4'-benzophenonetetracarboxylic dianhydride, 33 g of 4,4'-diaminodiphenyl ether as an amine, and the following formula % were added to N-methylpyrrolidone, and the mixture was heated at 20°C. The mixture was allowed to react for 6 hours.

60 g of N-methylolacrylamide was added to the obtained polyamic acid and reacted at 80°C for 1 hour. The molecular weight of the obtained polymer was 23,000, which was as expected.

5- Next, 3 g of 2-(p-dimethylaminostyryl)penzoxazole as a sensitizer and 6 g of 3-phenyl-5-isoxacilone as an initiator were added and mixed and dissolved at room temperature to form a photosensitive resin composition. I got something.

(The smoothed composition was applied to an aluminum plate using a spinner and dried at 65°C for 1 hour using a dryer.

This film is coated with Kodak Photographic Step Tablet 1-No.2.
/f2, so the larger the residual stage after development, the better the sensitivity).

Next, this was set in a spray developing machine, developed using a developer containing 60% by weight of N-methylpyrrolidone and 40% by weight of xylene, and further rinsed with isopropyl alcohol. When the pattern remained up to 13 steps, it showed high sensitivity. It turned out that.

Development time was only 30 seconds.

Next, the solution was coated on a silicon wafer in the same manner as described above, exposed to light over the entire surface, developed and rinsed, and further heat-cured at 150.250.350'C for 30 minutes each.

For the adhesion test, 100 pieces were cut into 1n+m square pieces and an attempt was made to peel them off using cellophane tape, but not a single piece was peeled off, indicating that the pieces had high adhesion.

Separately, it was coated on an aluminum plate, exposed to light over the entire surface, developed, rinsed, and cured with heat, and then the aluminum plate was removed by etching to obtain a film.

Tensile strength of the obtained film (JIS K-6760)
was as large as 14 Kg/mm2 (the higher the better), and the thermal decomposition initiation temperature was as high as 430°C (the higher the better).

Volume resistivity of the obtained film (JISC-6481)
is as large as 3X10"Ω・cm (the larger the better), and the dielectric constant is as low as 3.2 (LMHz) (the lower the better)
.

Comparative Examples 1 to 6 The same experiments as in Example 1 were carried out by changing the types and amounts of the sensitizer and initiator, and the results shown in Table 1 were obtained.

In Comparative Example 1, the amount of initiator added was 0.6 parts by weight, and the photosensitivity was extremely low.

In Comparative Example 2, the amount was 36 parts by weight, contrary to Comparative Example 1, and in this case, the initiator remained in the film, resulting in a low thermal decomposition initiation temperature.

Comparative Example 3 used an initiator other than the one according to the invention, had low photosensitivity, and was not practical.

In Comparative Example 4, the amount of sensitizer added was 0.3 parts by weight, and in this case, the photosensitivity was extremely low and the crosslinking was insufficient.

In Comparative Example 5, the amount of sensitizer was 33 parts by weight, and in this case, the amount of light transmitted to deep parts was insufficient, curing in deep parts was insufficient, voids were generated, and a uniform film was not obtained. .

Comparative Example 6 used a sensitizer other than the one of the present invention and had low photosensitivity, making it impractical.

Comparative Example 7 After dissolving 57 g of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride and 48 g of 2-hydroxyethyl methacrylate in γ-butyrolactone, 30 g of pyridine was added as a catalyst, and the mixture was heated at 20°C. The mixture was reacted for 24 hours to obtain an esterified product. Next, after adding 73 g of dicyclohexylcarbodiimide as an amidation catalyst, 4,
33 g of 4'-diaminodiphenyl ether and 10 g of the silicone diamine described in Example 1 were added and reacted at 20°C for 8 hours. Next, this slurry is filtered and
The filtrate was added dropwise to 70 liters of ethanol with vigorous stirring to precipitate a polymer, and then allowed to stand for 12 hours. The precipitate was filtered off, dried and ground. The obtained polymer (
The molecular weight of the photosensitive resin of formula (IV) was 6,500, which was much smaller than expected. Therefore, a polymer was synthesized again using the same method, but in this case too, the molecular weight was 11,000.
I stayed there. It was found that this method not only requires a long and complicated process, but also has large variations.

Next, this polymer was dissolved in N-methyl-2-pyrrolidone, and the same sensitizer and initiator as in Example 1 were added to obtain a photosensitive resin composition, which was then coated, exposed, and developed in the same manner. did.

In this case, spray development is possible 29- The developing time was 30 seconds, and the sensitivity was as high as IO steps.

However, when an attempt was made to heat-treat and evaluate the film in the same manner as in Example 1, the tensile strength of the film was 3K.
g/mm2 or less, and reliability could not be evaluated.

Comparative Example 8 60 g of diethylamino methacrylate was added to the polyamic acid in Example 1 and mixed at room temperature (formula [v]
photosensitive resin). Next, the same amounts of the same sensitizer and initiator as in Example 1 were added to obtain a photosensitive resin composition. An attempt was made to apply this composition to a silicon wafer, expose it to light, and develop it, but during spray development, not only the unexposed areas but also the exposed areas were dissolved, and no relief pattern could be obtained.

0 [Effects of the Invention] According to the present invention, it has become possible to obtain a photosensitized composition that can exhibit the inherent properties of a polyimide resin rich in heat resistance.

Moreover, since the method is simple, there is no variation, and since spray development is possible in the processing process, it has excellent processability and can be flowed in a 4-line process.

Furthermore, they discovered a special combination of sensitizer and initiator that has extremely high photosensitivity, making it possible to obtain good patterns with a small irradiation dose (which speeds up the process).

Claims (1)

[Claims] (1) Polymer (A) whose main component is a structural unit represented by the following formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [I] (In the formula, R_1, R_2: aromatic cyclic group, R_3: - H, -CH_3, -C_2H_5R_4:-
H, -CH_3, -C_2H_5, -CH_2OH, -
C_6H_5 n: 1-2, m: 0-2) Styryl compound (B) represented by the following formula [II] ▲ Formula,
There are chemical formulas, tables, etc.▼‐‐‐‐‐[II] (In the formula, R_5: -H, -CH_3, -C_2H_5, -
C_6H_5, R6: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲ Mathematical formulas, chemical formulas,
There are tables etc.▼(R:H, CH_3, C_2H_5)
Oxazolone compound (C) represented by the following formula [III]▲
There are mathematical formulas, chemical formulas, tables, etc. ▼‐‐‐‐‐[III] (R7 in the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc.) , -C_2H_5, -C_3
H_7, -C_4H_9, -C_6H_5, -OH, -
OCH_3, -OC_2H_6, -OC_3H_7, -
OC_4H_9, -OC_6H_5, -CH_2C_6
H_5, -CH_2CH_2C_6H_5, -CH_2
OH, -CH_2CH_2OH, -CH_2CH_3,
-CH(CH_3)_2, -C(CH_3)_3, -C
OCH_3, -COC_2H_5, -OCOCH_3,
-OCOC_2H_5, -CH_2NH_2, -CH_
2CH_2NH_2, -CONH_2, -CONHCH
_3, -CON(CH_3)_2, -CONHC_2H
_5, -CON(C_2H_5)_2, -NHCH_3
, -N(CH_3)_2, -N(C_2H_5)_2)
is an essential component, and (B) 1 per 100 parts by weight of (A)
~10 parts by weight and (C) 1 to 20 parts by weight.