JPH07330814A - Photoinitiator, photosensitive composition, photosensitive material and production of relief pattern - Google Patents

Abstract

PURPOSE:To obtain a photoinitiator, containing a specific benzalacetophenone compound, a titanocene compound and an N-aryl-alpha-amino acid and capable of manifesting excellent photosensitive characteristics and producing a pattern good in heat resistance and shape. CONSTITUTION:This photoinitiator contains a benzalacetophenone compound of formula I (R<1> to R<10> are each H, a 1-5C alkyl, amino substituted with are or two of alkyls, phenyl, NO2, etc.), a titanocene compound of formula II (R<11> to R<20> are each H, a halogen, a 1-20C alkoxy or a heterocyclic ring), an N-aryl- a-amino acid of formula III (R<21> to R<25> are each H, a halogen, a 1-4C alkyl, etc., and at least one thereof is cyano or a l-4C alkyl sulfone; R<26> is H, a 1-12C alkyl, etc.; R<27> and R<28> are each H or a 1-8C alkyl). Furthermore, this photosensitive composition contains an addition polymerizable compound having >=100 deg.C boiling point under atmospheric pressure and the photoinitiator and this photosensitive material contains a polyamide, a compound having carbon double bond and amino group and the photoinitiator. A relief pattern is obtained by irradiating the photosensitive material with active rays.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photoinitiator, a photosensitive composition, a photosensitive material and a method for producing a relief pattern.

[0002]

2. Description of the Related Art A polyimide or its precursor, which itself has a photopatterning property, is called a photosensitive polyimide and is used for a surface protective film of a semiconductor. Several methods of imparting photosensitivity are known for photosensitive polyimide. The representative one is Japanese Patent Publication Sho 55-
And a polyamic acid ester with a hydroxy acrylate as proposed in Japanese Patent No. 41422,
It is known that a polyamic acid as proposed in JP-A-54-145794 is blended with a compound such as amino acrylate and a photosensitive group is introduced by a salt bond.
In the former case, the photo-patterning property is relatively excellent, but it has a drawback that the film characteristics are inferior because it is difficult to increase the molecular weight and the removal of the photosensitive group tends to be incomplete.
Further, in the latter case, although a high molecular weight is easily obtained and the photosensitive group is easily volatilized, the film characteristics are excellent, but there is a drawback that the photo patterning property is not sufficient. In particular, for the photosensitive polyimide for thick film having a film thickness of 5 μm or more after curing, i-line stepper (using 365 nm light) and g-line stepper (using 435 nm light), and mirror projection type of all wavelengths of mercury lamp are used. There was a problem that good patterning property could not be obtained when exposed by an exposure machine.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the conventional techniques as described above, and a photoinitiator for producing a photosensitive composition and a photosensitive material exhibiting excellent photosensitive characteristics. The present invention provides an agent, a photosensitive composition using the same, a photosensitive material and a method for producing a relief pattern.

[0004]

The present invention has the following general formula (I):

[Chemical 4] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R
⁹ and R ¹⁰ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, 1
~ Amino group substituted with 2 to 1 carbon atoms alkyl group, 1 to 2 substituted with phenyl group, 1 to 5 carbon atoms alkoxy group, 1 carbon atom to 1 to 5 carbon atoms Represents a carbonylamino group substituted with an alkyl group, a phenyl group, a nitro group, a halogen atom or a thioalkyl group having 1 to 5 carbon atoms)),
The following general formula (II)

[Chemical 5] (In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ ,
R ¹⁸ , R ¹⁹ and R ²⁰ represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocycle) and a general formula (III) below.

[Chemical 6] (In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms,
A halogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or an alkylsulfone group having 1 to 4 carbon atoms, wherein R ²¹ ,
At least one of R ²² , R ²³ , R ²⁴ and R ²⁵ represents a cyano group or an alkylsulfone group having 1 to 4 carbon atoms;
²⁶ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, and 1 to 12 carbon atoms.
Represents an aminoalkyl group or an aryl group of R ²⁷ and R
²⁸ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and is related to a photoinitiator containing an N-aryl-α-amino acid.

The photosensitive composition and photosensitive material of the present invention described below may further contain other photoinitiators, if necessary. Other photoinitiators include, for example, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2
-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenyl disulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, N-phenyldiethanolamine, 2- (o- Ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,3 ′, 4,4′-
Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone. There is no particular limitation on the amount of these photoinitiators used.

The present invention also relates to a photosensitive composition containing an addition-polymerizable compound having a boiling point of 100 ° C. or higher at atmospheric pressure and the above photoinitiator.

The present invention also relates to a light-sensitive material containing a polyamide, a compound having a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof, and the above-mentioned photoinitiator. Regarding The present invention also relates to a method for producing a relief pattern, which comprises irradiating an actinic ray from a mask having a pattern formed on the coating film of the above-mentioned light-sensitive material, and developing and removing an unirradiated portion.

Examples of the benzalacetophenone compound represented by the above general formula (I) include benzalacetophenone, 4'-dimethylaminobenzalacetophenone,
4'-methoxybenzalacetophenone, 2 ', 4'-
Dimethoxybenzalacetophenone, 4'-ethoxybenzal-4-methoxyacetophenone, 4 '-(N, N
-Diallylamino) benzalacetophenone, 4'-acetaminobenzal-4-methoxyacetophenone,
2 ', 4'-Dimethylaminobenzal-2,4-dimethylacetophenone, 4'-methoxybenzal-2,4-
Dimethylaminoacetophenone, benzal-4-dimethylaminoacetophenone, 4'-butoxybenzal-4
-Methylacetophenone, 4'-chlorobenzal acetophenone and the like. You may use these in combination of 2 or more types. The benzalacetophenone compound is
For example, it can be obtained by carrying out a condensation reaction between a corresponding substituted benzaldehyde and a substituted acetophenone compound.

An example of the titanocene compound represented by the above general formula (II) is bis (cyclopentadienyl)-
Bis [2,6-difluoro-3- (2- (1H-pill-
1-yl) ethyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2
-(1H-pyr-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1H-pyr-1-yl) methyl) phenyl] Titanium, bis (cyclopentadienyl)
-Bis [2,6-difluoro-3- (2- (1H-pyr-1-yl) propyl) ethyl] titanium, bis (cyclopentadiethynyl) -bis [2,6-difluoro-3-
(Pyrid-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-
(2,5-Dimethylpyri-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-diethylpyr-1-yl) phenyl] titanium, bis ( Cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-isopropylpyrid-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5
-Bisdimethylaminopyridin-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-dimethyl-3-methoxypyr-1-yl) phenyl] titanium , Bis (cyclopentadienyl) -bis [2,6-difluoro-3-ethoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-isopropoxyphenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3-n-propoxyphenyl] titanium and the like. You may use these in combination of 2 or more types.

Examples of the N-arylamino-α-amino acid represented by the above general formula (III) include N- (p-methylsulfonylphenyl) -N-methylglycine and N-
(P-Methylsulfonylphenyl) -N-ethylglycine, N- (p-methylsulfonylphenyl) -N-propylglycine, N- (p-methylsulfonylphenyl)
-N-butylglycine, N- (p-cyanophenyl)-
Glycine, N- (p-2'-cyanomethylsulfonylphenyl) -N-methylglycine, N- (p-2'-cyanomethylsulfonylphenyl) -N-ethylglycine,
N- (p-2'-cyanomethylsulfonylphenyl)-
N-propylglycine, N- (p-2'-cyanomethylsulfonylphenyl) -N-butylglycine, N- (p
-Ethylsulfonylphenyl) -N-methylglycine,
N- (p-ethylsulfonylphenyl) -N-ethylglycine, N- (p-ethylsulfonylphenyl) -N-
Propylglycine, N- (p-ethylsulfonylphenyl) -N-butylglycine, N- (p-2'-cyanoethylsulfonylphenyl) -N-propylglycine, N
-(P-2'-cyanoethylsulfonylphenyl) -N
-Ethylglycine, N- (p-2'-cyanoethylsulfonylphenyl) -N-propylglycine, N- (p-
2'-Cyanoethylsulfonylphenyl) -N-butylglycine, N- (p-cyanophenyl) -N-methylglycine, N- (p-cyanophenyl) -N-ethylglycine, N- (p-cyanophenyl)- N-propylglycine, N- (p-cyanophenyl) -N-butylglycine, N- (p-propylsulfonylphenyl) -N-methylglycine, N- (p-butylsulfonylphenyl)
-N-methylglycine, N- (p-carboxamidophenyl) -N-methylglycine, N- (p-carboxamidophenyl) -N-ethylglycine, N- (p-carboxamidophenyl) -N-propylglycine , N
-(P-Carboxamidophenyl) -N-butylglycine, N- (p-ethoxycarbonylphenyl) -N-
Methylglycine, N- (p-ethoxycarbonylphenyl) -N-ethylglycine, N- (p-ethoxycarbonylphenyl) -N-propylglycine, N- (p-ethoxycarbonylphenyl) -N-butylglycine, N
-(P-methoxycarbonylphenyl) -N-methylglycine, N- (p-methoxycarbonylphenyl) -N
-Ethylglycine, N- (p-methoxycarbonylphenyl) -N-propylglycine, N- (p-methoxycarbonylphenyl) -N-butylglycine and the like. You may use these in combination of 2 or more types. The N-aryl-α-amino acid can be obtained, for example, by carrying out an aromatic nucleophilic substitution reaction of a corresponding substituted halobenzene and a glycine compound.

The use ratio of the above-mentioned benzalacetophenone compound, titanocene compound and N-aryl-α-amino acid is not particularly limited, but usually N-aryl-α.
-Use amino acids and titanocene compounds in higher proportions than benzalacetophenone compounds.

The addition-polymerizable compound contained in the photosensitive resin composition of the present invention has a boiling point of 100 ° C. or higher at normal pressure. When the boiling point is lower than 100 ° C. under normal pressure, the addition-polymerizable compound volatilizes and is not preferable in removing the solvent contained in the system by drying or irradiating with actinic rays. Further, the addition-polymerizable compound is preferably soluble in a commonly used organic solvent in order to form a uniform composition with the photoinitiator and the like.

Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol monomethyl ether, xylene, tetrahydrofuran. , Dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, N-
Methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethylene carbonate, propylene carbonate, sulfolane and the like can be mentioned.

The addition-polymerizable compound having a boiling point of 100 ° C. or higher under normal pressure is, for example, a compound obtained by condensing a polyhydric alcohol and an α, β-unsaturated carboxylic acid, such as ethylene glycol di (meta). ) Acrylate (meaning diacrylate or dimethacrylate, the same applies hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate,
1,2-propylene glycol di (meth) acrylate, di (1,2-propylene glycol) di (meth) acrylate, tri (1,2-propylene glycol) di (meth) acrylate, tetra (1,2-propylene glycol) ) Di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-
Vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide,
N-methylol acrylamide etc. are mentioned, and these may combine 2 or more types.

From the viewpoint of photosensitivity and film strength, the photoinitiator is preferably used in an amount of 0.01 to 30% by weight with respect to the addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure, More preferably, it is used in an addition amount of 05 to 10% by weight.

The photosensitive composition of the present invention may optionally contain one or more high molecular weight organic polymers. The weight average molecular weight of such a high molecular weight organic polymer is 10,000 to 700,000 from the viewpoint of pattern shape, mechanical strength and the like.
00 is preferable and 10,000 to 200,000
More preferably, those of 10,000 to 70,000 are particularly preferable. As the high molecular weight organic polymer, for example, the following ones are used.

(A) Copolyester Polyhydric alcohol such as diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol and the like and polyvalent carboxylic acid such as terephthalic acid, isophthalic acid, sebacic acid and adipine. A copolyester produced from acids, etc.

(B) Vinyl Polymer Methacrylic acid, acrylic acid, methacrylic acid or alkyl esters of acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-dimethylaminoethyl (meth)
A homopolymer or copolymer of vinyl monomers such as acrylate and 2-ethylhexyl (meth) acrylate.

(C) Polyformaldehyde (D) Polyurethane (E) Polycarbonate (F) Polyamide

(G) Polyamic Acid Polyamic acid can be obtained by addition polymerization using the following tetracarboxylic acid dianhydride and diamine compound. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-
Biphenyltetracarboxylic dianhydride, 1,2,5,6
-Naphthalenetetracarboxylic dianhydride, 2,3,6
7-naphthalenetetracarboxylic dianhydride, 2,3
5,6-Pyridine tetracarboxylic dianhydride, 1,4
5,8-naphthalenetetracarboxylic dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride,
4,4'-sulfonyldiphthalic dianhydride, m-terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, p-terphenyl-3,3 ", 4,4"- Tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 1,1,1,3,3,3-hexafluoro-2,2
-Bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)
Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3
3-hexafluoro-2,2'-bis [4- (2,3-
Dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,
2'-bis [4- (3,4-dicarboxyphenoxy)
Phenyl] propane dianhydride. Examples of the diamine compound include p-phenylenediamine and m-
Phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 4,4 ′ (or 3,4 ′) -, 3,
3'-, 2,4 '-)-diaminodiphenylmethane,
4,4 '(or 3,4'-, 3,3'-, 2,4'-)
-Diaminodiphenyl ether, 4,4 '(or 3,
4'-, 3,3'-, 2,4 '-)-diaminodiphenyl sulfone, 4,4' (or 3,4'-, 3,3 '
-, 2,4 '-)-diaminodiphenyl sulfide,
4,4'-benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-di (4-aminophenoxy) phenyl sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane,
2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4' -Diaminodiphenylmethane, 4,4'-
Di (3-aminophenoxy) phenyl sulfone, 3,
Aromatic diamines such as 3'-diaminodiphenyl sulfone and 2,2'-bis (4-aminophenyl) propane,
2,6-diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, 2,7-diaminobenzofuran, 2,7-diaminocarbazole,
3,7-diaminophenothiazine, 2,5-diamino-
1,3,4-thiadiazole, 2,4-diamino-6-
Examples thereof include heterocyclic diamines such as phenyl-s-triazine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine, and aliphatic diamines such as diaminopolysiloxane shown below.

[Chemical 7] (M and n represent an integer of 1 to 10) The above tetracarboxylic dianhydride and diamine compound may be used alone or in combination of two or more kinds.

(H) Cellulose ester For example, methyl cellulose, ethyl cellulose

By adding a high molecular weight organic polymer to the photosensitive composition, properties such as adhesion to a substrate, chemical resistance and film property can be improved. This high molecular weight organic polymer has a photocurability of 20 to 8 based on the total weight of the high molecular weight organic polymer and the addition-polymerizable compound.
It is desirable to set it in the range of 0% by weight.

The photosensitive composition of the present invention may also contain coloring substances such as dyes and pigments, if necessary. Examples of coloring substances include fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria pure blue, malachite green, and night green B,
Examples include spirone proof.

The photosensitive composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibition inhibitor in order to enhance stability during storage. Examples of such substances include p-methoxyphenol, p-benzoquinone, hydroquinone, pyrogallol, naphthylamine, phenothiazine, aryl phosphite, and nitrosamine.

The photosensitive composition of the present invention may contain other additives known to be used in photosensitive resin compositions, for example, additives such as plasticizers and adhesion promoters.

The photosensitive composition of the present invention is applied onto a substrate such as a silicone wafer, a metal substrate, a glass substrate or a ceramic substrate by a dipping method, a spray method, a screen printing method, a spin coating method, etc. By heating and drying the part, a coating film having no tackiness can be obtained. This coating film is exposed to actinic rays or actinic rays through a mask on which a desired pattern is drawn. Examples of the actinic ray or actinic ray to be applied include ultraviolet rays, far ultraviolet rays, visible light, electron rays, and X-rays. After irradiation, the non-irradiated portion is dissolved and removed with an appropriate developing solution to obtain a desired relief pattern. As the developing solution, N, N-dimethylformamide,
A good solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone or a mixed solvent thereof with a poor solvent such as lower alcohol, water or aromatic hydrocarbon is used. After development, rinse with a poor solvent, etc., if necessary and at 100 ° C.
Drys before and after to make the pattern stable.

The light-sensitive material of the present invention comprises the above polyamide,
A compound and a photoinitiator having a carbon-carbon double bond and an amino group or a quaternized salt thereof which are dimerizable or polymerizable by actinic radiation in an addition-polymerizable compound having a boiling point of 100 ° C. or higher under normal pressure. Is included. The use ratio of these is the same as in the case of the photosensitive composition.

When the polyamide is a polyamic acid, a compound having a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof is used.
From the viewpoint of characteristics, it is preferable to use an amount that is equimolar to the carboxyl group of the polyamic acid.

The light-sensitive material may contain a bisazide compound, and examples of the bisazide compound include

[Chemical 8]

[Chemical 9] Etc. The bisazide compound is preferably used in the range of 0.01 to 10% by weight with respect to the polyamide.

Examples of the compound having a carbon-carbon double bond and an amino group or a quaternized salt thereof which can be dimerized or polymerized by actinic radiation contained in the light-sensitive material include the following compounds.

[Chemical 10]

[0031]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of 4'-Dimethylaminobenzalacetophenone (Compound No. 1) 4-Dimethylaminobenzaldehyde (14.9 g,
0.1 mol) and acetophenone (1.20 g, 0.1 mo)
l) was put in a flask, 100 ml of ethanol was further added, a water flow cooling tube, a mechanical stirrer and a dropping funnel were set, heated at an oil temperature of 60 ° C., and 10 g of a 10 wt% sodium hydroxide aqueous solution was added while stirring well. hand,
The mixture was heated under reflux for 2 hours. After allowing to cool, it was neutralized with a 10% by weight aqueous solution of hydrochloric acid, the resulting precipitate was filtered off, washed with water several times, and washed.
It was dried in a vacuum dryer overnight. The obtained yellow powder had a melting point of 114.0 ° C. Yield 22.3 g (89
%)Met.

Synthesis Example 2 Synthesis of 4'-acetaminobenzal-4-methoxyacetophenone (Compound No. 2) 4-acetaminobenzaldehyde (1.63 g, 0.
1 mol) and 4-methoxyacetophenone (1.50 g,
0.1 mol) in a flask and 100 ml of ethanol
Was further added, a water cooling tube, a mechanical stirrer and a dropping funnel were set, the oil temperature was heated to 60 ° C., 10 g of a 10 wt% sodium hydroxide aqueous solution was added while stirring well, and the mixture was heated under reflux for 2 hours. After cooling, the mixture was neutralized with a 10 wt% hydrochloric acid aqueous solution, the generated precipitate was filtered off, washed with water several times, washed, and dried overnight in a vacuum dryer. The resulting yellow powder had a melting point of 180.0 ° C. Yield 24.2g
(82%).

Synthesis Example 3 N- (4-cyanophenyl) glycine (Compound No. 3)
Synthesis of 4-cyanoaniline (100 g, 0.847 mol) was placed in a flask, 300 ml of water was further added, and a water cooling tube,
Set a mechanical stirrer and a dropping funnel, heat at an oil temperature of 100 ° C., and while stirring well, add an aqueous solution of monochloroacetic acid (104 g, 1.12 mol) (150 ml of water) over about 30 minutes, and further add 2.5 Heated to reflux for hours. After cooling, about 100 ml of ethyl acetate was added to dissolve the insoluble matter, and the organic layer was separated with a separating funnel. The remaining water layer and the water layer obtained by extracting the organic layer with 100 ml of 5% aqueous sodium hydroxide solution were combined, acidified with 1/10 N hydrochloric acid, the precipitate formed was filtered off, and washed with water several times. Washed. After heating and drying in an oven at 60 ° C. for 3 hours, it was dried overnight in a vacuum desiccator. The white powder obtained had a melting point of 240.3 ° C. The yield is 38.8 g (26
%)Met.

Synthesis Example 4 Synthesis of N- (4-cyanophenyl) -N-methylglycine (Compound No. 4) 4-Fluorobenzonitrile (10.44 g, 0.08)
6 mol), N-methylglycine (8.45 g, 0.09)
5 mol) and potassium carbonate (14.28 g) were added to the flask, 200 ml of dimethyl sulfoxide was further added as a solvent, and the mixture was heated in a 100 ° C. oil bath for 9 hours while stirring with a magnetic stirrer with a water cooling tube. After allowing to cool, it was dissolved in 1 liter of water, acidified with 1/10 N hydrochloric acid, and the precipitate was filtered off. After washing well with water, hexane /
It was further washed with benzene (volume ratio 4/1). The yield of the dried product was 14.21 g (yield 86.7%), and the melting point was 64.5 ° C. The structures of Compound Nos. 1, 2, 3 and 4 were confirmed by ¹ H-NMR spectrum. ¹
H-NMR data are shown in Tables 1 to 3.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

Comparative Examples 1 to 3 and Examples 1 to 5 N-methyl-2, a polyamic acid obtained by reacting 4,4'-diaminodiphenyl ether and pyromellitic dianhydride in equimolar amounts by a conventional method. -Pyrrolidone solution 10g
(Solid content 20% by weight), 1.8 g of dimethylaminoethyl methacrylate and a photoinitiator were mixed and then mixed with stirring to obtain a light-sensitive material. After filtering with a filter, it was spin coated on a silicon wafer. Then on the hot plate 10
It heated at 0 degreeC for 200 second, the solvent was dried, and it was set as the photosensitive coating film. The film thickness after drying was 20 microns. Pattern exposure was performed on the coating film through a photomask with a mirror projection exposure machine using an ultra-high pressure mercury lamp as a light source. The exposure amount at this time was 500 mJ / cm ² . After that, immersion development was performed with a mixed solution of N-methyl-2-pyrrolidone and methyl alcohol (volume ratio: 4/1). Further rinsed with isopropanol. The residual film rate obtained by measuring and observing the pattern shape after development (value obtained by dividing the film thickness by the initial film thickness)
Table 4 shows the minimum opening through hole diameter (opening diameter).

[0039]

[Table 4]

For the wafer of Example 4, this was placed in a nitrogen atmosphere at 100 ° C. for 15 minutes, 200 ° C. for 20 minutes, and 3
It heated at 50 degreeC for 60 minutes, and was set as the final cured film. A good polyimide pattern with a final cured film thickness of 10 microns was obtained.
As shown in the examples, the photosensitive composition of the present invention has excellent photosensitivity as compared with the composition of the comparative example.

Examples 6 to 11 and Comparative Examples 4 to 6 The same tests are conducted on the light-sensitive materials obtained by adding the bisazide compound to the compounding compositions similar to those of Examples 1 to 5 and Comparative Examples 1 to 3. The results are shown in Table 5 together with the composition.

[0042]

[Table 5]

As shown in the examples, the residual film rate after development was improved by further adding the bisazide compound.

[0044]

The photoinitiator of the present invention makes it possible to obtain a photosensitive composition and a photosensitive material exhibiting excellent photosensitivity. With this photosensitizer, a pattern having excellent properties such as heat resistance and shape can be produced. be able to.

Claims (5)

[Claims] 1. The following general formula (I): (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R
⁹ and R ¹⁰ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, 1
~ Amino group substituted with 2 to 1 carbon atoms alkyl group, 1 to 2 substituted with phenyl group, 1 to 5 carbon atoms alkoxy group, 1 carbon atom to 1 to 5 carbon atoms Represents a carbonylamino group substituted with an alkyl group, a phenyl group, a nitro group, a halogen atom or a thioalkyl group having 1 to 5 carbon atoms)),
The following general formula (II): (In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ ,
R ¹⁸ , R ¹⁹ and R ²⁰ represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or a heterocycle, and a titanocene compound represented by the following general formula (III): (In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms,
A halogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or an alkylsulfone group having 1 to 4 carbon atoms, wherein R ²¹ ,
At least one of R ²² , R ²³ , R ²⁴ and R ²⁵ represents a cyano group or an alkylsulfone group having 1 to 4 carbon atoms;
²⁶ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, and 1 to 12 carbon atoms.
Represents an aminoalkyl group or an aryl group of R ²⁷ and R
²⁸ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), which is a photoinitiator containing an N-aryl-α-amino acid. 2. A photosensitive composition comprising an addition-polymerizable compound having a boiling point of 100 ° C. or higher at atmospheric pressure and the photoinitiator according to claim 1. 3. A photosensitive material containing a polyamide, a compound having a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof, and the photoinitiator according to claim 1. 4. The photosensitive material according to claim 3, further containing a bisazide compound. 5. A method for producing a relief pattern, which comprises irradiating an actinic ray from a mask having a pattern drawn on the coating film of the photosensitive material according to claim 3 or 4 and developing and removing the unirradiated portion.