JP2002311574A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant photosensitive resin composition which has high adhesiveness to a substrate, has no problems such as precipitation, and exhibits good patterning performance. SOLUTION: The following general formula (1): (R1 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; R2 is a divalent organic group having 1 to 20 carbon atoms;
Represents a divalent organic group having 1 to 10 carbon atoms. R4 and R5 represent an organic group having 1 to 10 carbon atoms, and m represents an integer of 0 to 2. X
Represents a divalent organic group containing a carbonyl group. ), A photopolymerization initiator, a compound having an unsaturated double bond, and a diluting solvent, to produce a photosensitive resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-resistant resin used for forming a pattern of a heat-resistant resin material used for an insulating material of an electronic component or a passivation film, a buffer coat film, an interlayer insulating film, etc. in a semiconductor device. The present invention relates to a photosensitive resin composition containing an alkoxysilane compound suitable as an adhesive between a resin precursor and a substrate.

[0002]

2. Description of the Related Art Hitherto, a polyimide resin having excellent heat resistance, electrical characteristics and mechanical characteristics has been known as a surface protective film and an interlayer insulating film of a semiconductor element. This polyimide is
In general, it is provided in the form of a photosensitive polyimide precursor composition, which can be easily formed into a finely processed heat-resistant film by applying, patterning with active light, developing, and thermal imidization. The feature is that the process can be significantly shortened as compared with the non-photosensitive polyimide.

However, in the developing step, it is necessary to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution. Measures are being sought. In response to this, various proposals have recently been made for heat-resistant photosensitive resin materials that can be developed with a dilute alkaline aqueous solution, similarly to photoresists.

[0004] Among them, an alkali water-soluble polyhydroxyamide, for example, a polybenzoxazole (PBO) precursor is converted to a photoactive component (PA) such as quinonediazide (NQD).
Recently, attention has been paid to a method of using it in combination with C) (Japanese Patent Publication No. 1-46862, Japanese Patent Application Laid-Open No. 63-96162). According to these methods, pattern formation is easy and storage stability is good, and since a thermosetting film property equivalent to polyimide is obtained, it is attracting attention as a promising alternative material of an organic solvent developable polyimide precursor. I have. In addition, a combination of a polymer having a phenolic hydroxyl group introduced into the main chain and PAC (Japanese Patent Application Laid-Open No. H11-106651) and a combination of a polymer having a phenolic hydroxyl group introduced into the side chain thereof and PAC (Japanese Patent Publication No. 2890213) Has been proposed.

[0005] However, there are still many problems in the adhesiveness between the substrate and the coating film pattern of the heat-resistant photosensitive resin obtained by the method disclosed so far. Especially when an aqueous alkali solution is used as a developer,
Since the heat-resistant photosensitive resin pattern formed by light has a relatively high affinity for an alkaline aqueous solution, the alkaline aqueous solution may easily enter the adhesive interface and be easily peeled off during development, so that normal patterning may not be performed. In order to improve the adhesion between the coating film of the heat-resistant photosensitive resin and the substrate, a method of pre-treating the substrate in advance,
Examples include a method of adding an adhesive such as a silane coupling agent to the precursor varnish, and a method of adding or copolymerizing an adhesive unit such as an organosilicon compound to a polymer. Among these methods, particularly, a method of internally adding an adhesive to a varnish has been frequently used recently because it is simple and can simplify the process. As a method using such an internally added adhesive, for example, a method using a silane coupling agent containing a highly reactive isocyanate group (JP-A-11-338157, JP-A-2000-122299) ), A method using a silane coupling agent containing a highly polar group (JP-A-2000-187321), and the like.

However, these internally added adhesives are satisfactory in that the adhesive does not efficiently collect at the interface or that the adhesive is deposited because of lack of compatibility with the heat-resistant photosensitive resin. In many cases, good adhesion cannot be obtained. Further, in some photosensitive systems, polar groups contained in the adhesive may significantly lower the sensitivity. In any case, a high-performance bonding system that ensures good adhesiveness while maintaining good compatibility with the heat-resistant photosensitive resin and that does not lower sensitivity has not been obtained.

[0007]

SUMMARY OF THE INVENTION The present invention, as an additive component of a heat-resistant photosensitive resin composition, has high adhesion to a substrate, has no problems such as deposition, and can exhibit good patterning performance. An object of the present invention is to provide such an adhesive and a heat-resistant photosensitive resin composition using the same.

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on various organosilicon compounds. As a result, an alkoxysilane having a structure in which a sulfur atom and a carbonyl group are not adjacent to each other in a molecule is obtained. By adding the compound to the heat-resistant photosensitive resin precursor, furthermore, a photopolymerization initiator, by compounding a compound having an unsaturated double bond to form a photosensitive resin composition, found that the above properties are satisfied, The present invention has been made.

That is, a first aspect of the present invention is to provide a heat-resistant resin precursor and an alkoxysilane compound represented by the following general formula (1):

[0010]

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(R1 is a hydrogen atom or a group having 1 to 20 carbon atoms.
R2 is a divalent organic group having 1 to 20 carbon atoms, and R3 is a divalent organic group having 1 to 10 carbon atoms.
R4 and R5 represent an organic group having 1 to 10 carbon atoms, and m represents an integer of 0 to 2. X represents a divalent organic group containing a carbonyl group. A photosensitive resin composition comprising a photopolymerization initiator, a compound having an unsaturated double bond, and a diluting solvent.

A second aspect of the present invention is the photosensitive resin composition according to claim 1, wherein said alkoxysilane compound is represented by the following general formula (2).

[0013]

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[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The alkoxysilane compound in the present invention may be a commercially available product, or may be obtained by synthesizing a commercially available raw material. For example, by reacting one equivalent of an amine compound containing a sulfur atom in a molecule and one equivalent of an alkoxysilane compound having an isocyanate group in a suitable solvent, a compound of the general formula (2) can be obtained.

X in the general formula (1) is a divalent organic group containing a carbonyl group, specifically, a ketone group, a urea group, an ester group, an amide group, a urethane group, a thiourea group, a thioester group, a carbonate group. And an acid anhydride group, but a urea group and a urethane group are particularly preferable. Further, as the alkoxysilane compound having an isocyanate group used to obtain (2), a compound represented by the following general formula (3) is preferably used.

[0016]

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Among these, particularly preferred compounds include the following.

[0018]

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The solvent used for synthesizing the alkoxysilane compound is preferably one that dissolves both the amine compound and the isocyanate group-containing alkoxysilane compound as raw materials, and includes N, N-dimethylformamide (DMF), N, N -Dimethylacetamide (DMA
c), N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), γ-butyrolactone (GB
L), dimethyl sulfoxide (DMSO), N, N'-
Dimethylimidazolidinone (DMI), diethylene glycol dimethyl ether (diglyme), tetrahydrofuran (THF), cyclohexanone, ethyl lactate, propylene glycol monomethyl ether acetate (P
GMEA) and the like.

In order to accelerate the reaction when synthesizing the present compound, a tin compound such as dibutyltin dilaurate or dibutyltin diacetate can be used as a catalyst. The alkoxysilane compound synthesized in this manner is used by isolating it by a method such as concentration, distillation or recrystallization, or by directly adding the reaction solution or diluting it with a solvent and adding it to the photosensitive resin composition. I can do it.

The alkoxysilane compound of the present invention is suitably used as a component of a negative photosensitive resin composition comprising an alkali-soluble polymer, a monomer containing an unsaturated double bond, and a photopolymerization initiator. Examples of such an alkali-soluble polymer include a polyamide acid ester of a polyimide precursor and a hydroxypolyamide of a polybenzoxazole precursor. The latter is particularly useful when it has a phenolic hydroxyl group and has the following structure (4) in which it is partially replaced by a group containing an unsaturated double bond.

[0022]

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Wherein R6 is a divalent aromatic group, R7 is a tetravalent aromatic group, and n is an integer of 2 to 150.
R8 and R9 are a hydrogen atom and / or a monovalent organic group having an unsaturated double bond represented by the following general formula (5), and R8 and R9 may be the same or different. , R8 + R9 = 100 mol%, at least 10 mol% or more of R8 and R9;
0 mol% or less is a monovalent organic group having an unsaturated double bond represented by the general formula (5))

[0024]

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(Wherein, R10 is a hydrogen atom and / or an aliphatic group having 1 to 3 carbon atoms, and R11 and R12 are each independently a hydrogen or an alkyl group. P is 2 to 10)
Is an integer of

The compound having an unsaturated double bond used as a component of the photosensitive resin composition of the present invention is preferably a (meth) acrylic compound polymerizable by a photopolymerization initiator. Diacrylate (each 2 to 2 ethylene glycol units)
0), polyethylene glycol dimethacrylate (each 2 to 20 ethylene glycol units), poly (1,2-
(Propylene glycol) diacrylate, poly (1,2-propylene glycol) dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, dipentaerythritol hexaacrylate, methylenebisacrylamide, N-methylolacrylamide , Ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, N, N'-di (2-methacryloxyethyl) urea and the like, but are not limited thereto. In use, they may be used alone or as a mixture of two or more.

The photopolymerization initiator used as a component of the photosensitive resin composition of the present invention includes, for example, (a) benzophenone, methyl o-benzoyl benzoate,
Benzophenone derivatives such as benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone (b) 2,2'-diethoxyacetophenone, 2-hydroxy-2-
Methylpropiophenone, acetophenone derivatives such as 1-hydroxycyclohexylphenyl ketone (c) thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone (d) benzyl, benzyldimethylketal, benzyl-β
Benzyl derivatives such as -methoxyethyl acetal

(E) Benzoin derivatives such as benzoin and benzoin methyl ether. (F) 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2
-(O-methoxycarbonyl) oxime, 1-phenyl-1,2
-Propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenyl-propanetrione-2-
Oximes such as (O-ethoxycarbonyl) oxime and 1-phenyl-3-ethoxy-propanetrione-2- (O-benzoyl) oxime, but are not limited thereto. In use, they may be used alone or as a mixture of two or more. Among the above photopolymerization initiators, the oximes (f) are more preferable, particularly in terms of photosensitivity.

A sensitizer for improving photosensitivity can be added to the photosensitive composition of the present invention, if desired. Such sensitizers include, for example, Michler's ketone, 4,
4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzylidene) cyclopentanone, 2,6-bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-dimethylamino Benzylidene) -4-methylcyclohexanone, 2,6-bis (4'-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, 2 -(4'-dimethylaminocinnamylidene indanone, 2- (4'-dimethylaminobenzylidene indanone, 2- (p-4'-dimethylaminobiphenyl) -benzothiazole, 1,3-bis (4-dimethyl Aminobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminokuma 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N -Ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, isoamyl 4-diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl -5-mercapto-1,
2,3,4-tetrazole, 2-mercaptobenzothiazole,
2- (p-dimethylaminostyryl) benzoxazole,
2- (p-dimethylaminostyryl) benzthiazole, 2-
(P-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like, but are not limited thereto. In use, they may be used alone or as a mixture of two or more.

In order to form a varnish of the heat-resistant photosensitive resin composition, a diluting solvent is used. As such a solvent component, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetramethylurea, N, N′-dimethylimidazolidinone, tetrahydrofuran (THF), cyclohexanone , Ethyl lactate, propylene glycol monomethyl ether acetate, and the like, but are not limited thereto. In use, they may be used alone or as a mixture of two or more.

A heat polymerization inhibitor can be added to the heat-resistant photosensitive composition of the present invention, if desired, to improve the viscosity of the composition solution during storage and the stability of photosensitivity. Examples of such a thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine,
Ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-t
ert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-
1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N- Nitroso-N
(1-Naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl-phenylmethane), etc. In addition, if necessary, a dye, a surface smoothness-imparting agent, etc. may be appropriately added. Can be done.

Examples of use of the heat-resistant photosensitive resin composition containing the alkoxysilane compound of the present invention are shown below. First, the composition is applied to a suitable support, for example, a silicon wafer, ceramic, or aluminum substrate. This coating method is performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after pre-baking at 80 to 120 ° C. and drying the coating film, contact aligner, mirror projection,
Irradiation with actinic radiation is performed using an exposure device such as a stepper. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used, but those having a wavelength of 200 to 500 nm are preferable. In terms of pattern resolution and handleability, the light source wavelength is preferably i-line, and the exposure apparatus is preferably a stepper.

Next, development is carried out, which can be carried out by selecting from methods such as an immersion method, a paddle method and a rotary spray method. Examples of the developer include an aqueous alkali solution, for example, inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine; tetramethylammonium hydroxide; An aqueous solution of a quaternary ammonium salt such as butylammonium hydroxide, and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added as necessary can be used. Organic solvent-based developers such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-
Pyrrolidone, tetramethylurea, γ-butyrolactone, dimethylsulfoxide (DMSO), tetrahydrofuran (THF), cyclohexanone, cyclopentanone and the like can also be used.

After development, the pattern film can be obtained by washing with a rinse solution and removing the developer. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol and the like can be used alone or in combination. The thus obtained pattern film of the heat-resistant resin precursor composition such as polyimide or polybenzoxazole is heated to 300 ° C. or more to volatilize the photosensitive component, and then proceed with the cyclization reaction. , Polyimide or polybenzoxazole. Such heating conversion can be performed by using a hot plate, an oven, and a temperature rising oven in which a temperature program can be set. Air may be used as the atmosphere gas when performing the heat conversion,
An inert gas such as nitrogen or argon can also be used.

Using the alkoxysilane compound of the present invention,
When the adhesiveness between the pattern film and the substrate was evaluated by observation with a microscope or the like by the above method, excellent adhesiveness was observed in both cases after development and after heat curing.
Hereinafter, examples of embodiments of the present invention will be described with reference to examples.

[Production Example 1] In a 2 L separable flask,
62.5 g of 2-aminobenzenethiol (0.50 mo
l), 400 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. A mixture of 123.6 g (0.50 mol) of 3-isocyanatopropyltriethoxysilane and 200 g of N-methyl-2-pyrrolidone was put into a dropping funnel, and slowly added dropwise to the solution at room temperature. After continuing stirring at room temperature for 3 hours, the reaction was confirmed by high performance liquid chromatography (HPLC).
No starting material was detected, and it was confirmed that the product was a single product (Compound A-1). [Using this reaction solution as an additive as it was, a heat-resistant photosensitive resin composition varnish was prepared, and patterning and adhesion evaluation were performed. (Example 1)]

[Production Example 2] In a 2 L separable flask,
38.6 g of 2-aminoethanethiol (0.50 mo
l), 300 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. A mixture of 123.6 g (0.50 mol) of 3-isocyanatopropyltriethoxysilane and 180 g of N-methyl-2-pyrrolidone was put into a dropping funnel, and slowly added dropwise to the above solution at room temperature. After stirring for 3 hours at room temperature, the reaction was confirmed by high performance liquid chromatography (HPLC).
No starting material was detected, and it was confirmed that the product was a single product (Compound A-2). [Using this reaction solution as an additive as it was, a heat-resistant photosensitive resin composition varnish was prepared, and patterning and adhesion evaluation were performed. (Example 2)]

[Production Example 3] 52.6 g (0.5 g) of 3-methylthiopropylamine was placed in a 2 L separable flask.
0 mol) and 300 g of N-methyl-2-pyrrolidone were added and dissolved by stirring. 123.6 g (0.50 mol) of 3-isocyanatopropyltriethoxysilane and N
-Methyl-2-pyrrolidone 180 g of a mixed solution was placed in a dropping funnel, and slowly added dropwise to the solution at room temperature.
After completion of the dropwise addition, stirring was continued at room temperature for 3 hours, and the reaction was confirmed by high performance liquid chromatography (HPLC). As a result, no starting material was detected and it was confirmed that the product was a single product (compound A- 3). [Using this reaction solution as an additive as it was, a heat-resistant photosensitive resin composition varnish was prepared, and patterning and adhesion evaluation were performed. (Example 3)]

[Production Example 4] In a 2 L separable flask, 133.8 g (0.50 mol) of 2- (2-aminoethylthioethyl) triethoxysilane and N-methyl-
300 g of 2-pyrrolidone was added and dissolved by stirring.
A mixed solution of 59.5 g (0.50 mol) of phenyl isocyanate and 180 g of N-methyl-2-pyrrolidone was put into a dropping funnel, and slowly added dropwise to the above solution at room temperature. After completion of the dropwise addition, the mixture was stirred at room temperature. After 3 hours, the reaction was confirmed by high performance liquid chromatography (HPLC). As a result, no starting material was detected, and it was confirmed that the product was a single product (Compound A-4). [Using this reaction solution as an additive as it was, a heat-resistant photosensitive resin composition varnish was prepared, and patterning and adhesion evaluation were performed. (Example 4)]

[Preparation Example 5] In a 2 L separable flask, 54.6 g (0.50 mol) of 2-aminophenol was added.
l), 300 g of N-methyl-2-pyrrolidone was added and dissolved by stirring. A mixture of 123.6 g (0.50 mol) of 3-isocyanatopropyltriethoxysilane and 180 g of N-methyl-2-pyrrolidone was put into a dropping funnel, and slowly added dropwise to the above solution at room temperature. After stirring for 3 hours at room temperature, the reaction was confirmed by high performance liquid chromatography (HPLC).
No starting material was detected, and it was confirmed that the product was a single product (Compound B-1). [Using this reaction solution as an additive as it was, a heat-resistant photosensitive resin composition varnish was prepared, and patterning and adhesion evaluation were performed. (Comparative Example 1) Examples of evaluation of the adhesiveness of the photosensitive resin composition using the alkoxysilane compounds obtained in the above Examples and Comparative Examples are shown below.

REFERENCE EXAMPLE (Synthesis of base polymer) N, N-dimethylacetamide (DMAc) was prepared in a separable flask having a capacity of 2 L.
370 g, pyridine 26.90 g (0.34 mol),
2,2-bis (3-amino-4-hydroxyphenyl)
61.53 g of hexafluoropropane (0.17 mo
1) was mixed and stirred at room temperature (25 ° C.) to dissolve the diamine. To this, 41.32 g (0.1%) of 4,4′-diphenylether dicarboxylic acid dichloride was separately added to 114 g of diethylene glycol dimethyl ether (DMDG).
(4 mol) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a 15-20 ° C. water bath. The time required for the dropwise addition was 20 minutes, and the reaction solution temperature was 30 ° C. at the maximum. The reaction solution was left to stir for 10 hours from the end of the dropping, and then the reaction solution was dropped into 5 L of water under high-speed stirring to disperse and precipitate the polymer. A hydroxypolyamide having a terminal was obtained. The weight average molecular weight was 10,300 (in terms of polystyrene).

(Synthesis of Photosensitive Group-Introduced Polymer) 100 g of the dried hydroxypolyamide obtained above was used in a volume of 1 L
Was re-dissolved by adding 400 g of γ-butyrolactone (GBL), and 0.55 g of dibutyltin dilaurate was added, followed by heating to 50 ° C. in an oil bath. Separately, 55.52 g of γ-butyrolactone (GBL) and 18.51 g of 2-isocyanatoethyl methacrylate (0.119 mol, corresponding to 35 mol% of the total hydroxyl groups of the polymer) were dissolved for 15 minutes. And dropped. After completion of the dropwise addition, the mixture was stirred at 50 ° C. for 4 hours.

After 4 hours, the reaction solution was deionized with deionized water.
8L, the polymer precipitated at that time was separated and washed, and then vacuum-dried at 50 degrees for 24 hours,
A photosensitive polybenzoxazole precursor (PB-1) was obtained. In this polymer, the isocyanate reacts with both the amino group at the polymer terminal and the hydroxyl group in the polymer, so that the methacrylate group is introduced via a urea bond at the polymer terminal and a urethane bond at the side chain. I have. According to the measurement of the proton-NMR spectrum of this polymer, the introduction rate of the entire methacrylate group was 2%.
It was confirmed to be 8.6%.

(Preparation of photosensitive resin composition)

Example 1 A photosensitive polybenzoxazole precursor (P
B-1) In 20 g, 4 g of tetraethylene glycol dimethacrylate, 4 g of N, N'-di (2-methacryloxyethyl) urea, 1-phenyl-1,2-propanedione-2- (O
-Benzoyl) oxime 1.2 g, Michler's ketone 0.4 g, N-nitrosodiphenylamine 0.01 g, and 6.0 g of the alkoxysilane compound solution (A-1) obtained in Production Example 1 were further added. N-methyl-2-
It was dissolved in 25 g of pyrrolidone to obtain a varnish-like photosensitive resin composition (PBN-A1).

[0045]

Example 2 A photosensitive polybenzoxazole precursor (P
B-1) In 20 g, 4 g of tetraethylene glycol dimethacrylate, 4 g of N, N'-di (2-methacryloxyethyl) urea, 1-phenyl-1,2-propanedione-2- (O
-Benzoyl) oxime 1.2 g, Michler's ketone 0.4 g, N-nitrosodiphenylamine 0.01 g, and 6.0 g of the alkoxysilane compound solution (A-2) obtained in Production Example 2 were further added. N-methyl-2-
It was dissolved in 25 g of pyrrolidone to obtain a varnish-like photosensitive resin composition (PBN-A2).

[0046]

Example 3 Photosensitive polybenzoxazole precursor (P
B-1) In 20 g, 4 g of tetraethylene glycol dimethacrylate, 4 g of N, N'-di (2-methacryloxyethyl) urea, 1-phenyl-1,2-propanedione-2- (O
-Benzoyl) oxime (1.2 g), Michler's ketone (0.4 g), N-nitrosodiphenylamine (0.01 g) and 6.0 g of the alkoxysilane compound solution (A-3) obtained in Production Example 3 were further added. N-methyl-2-
It was dissolved in 25 g of pyrrolidone to obtain a varnish-like photosensitive resin composition (PBN-A3).

[0047]

Example 4 A photosensitive polybenzoxazole precursor (P
B-1) In 20 g, 4 g of tetraethylene glycol dimethacrylate, 4 g of N, N'-di (2-methacryloxyethyl) urea, 1-phenyl-1,2-propanedione-2- (O
-Benzoyl) oxime 1.2 g, Michler's ketone 0.4 g, N-nitrosodiphenylamine 0.01 g and 6.0 g of the alkoxysilane compound solution (A-4) obtained in Production Example 4 were further added. N-methyl-2-
It was dissolved in 25 g of pyrrolidone to obtain a varnish-like photosensitive resin composition (PBN-A4).

[0048]

Comparative Example 1 A photosensitive polybenzoxazole precursor (P
B-1) In 20 g, 4 g of tetraethylene glycol dimethacrylate, 4 g of N, N'-di (2-methacryloxyethyl) urea, 1-phenyl-1,2-propanedione-2- (O
-Benzoyl) oxime 1.2 g, Michler's ketone 0.4 g, N-nitrosodiphenylamine 0.01 g and 6.0 g of the alkoxysilane compound solution (B-1) obtained in Production Example 5 were further added. N-methyl-2-
It was dissolved in 25 g of pyrrolidone to obtain a varnish-like photosensitive resin composition (PBN-B1).

[0049]

Comparative Example 2 Photosensitive polybenzoxazole precursor (P
B-1) In 20 g, 4 g of tetraethylene glycol dimethacrylate, 4 g of N, N'-di (2-methacryloxyethyl) urea, 1-phenyl-1,2-propanedione-2- (O
-Benzoyl) oxime (1.2 g), Michler's ketone (0.4 g), N-nitrosodiphenylamine (0.01 g), γ-methacryloxypropyltriethoxysilane (1.2 g), N-methyl-2-pyrrolidone 2
5 g of a varnish-shaped photosensitive resin composition (PBN).
-B2) was obtained.

The varnish-like solutions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were spin-coated on a 5-inch silicon wafer (Clean Track M manufactured by Tokyo Electron Limited).
ark 7), dried at 95 ° C. for 4 minutes,
A coating having a thickness of μm was obtained. This coating film is exposed by changing the exposure amount stepwise through a reticle using an i-line stepper exposure machine NSR1755i7B (manufactured by Nikon Corporation), and the wafer is exposed to a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Clariant Japan KK). AZ30
(0MIF) until the unexposed portion was completely dissolved, and then rinsed with pure water to obtain a negative pattern. The minimum exposure required to obtain a pattern (the minimum exposure required), the critical resolution at the time of the required minimum exposure (critical resolution), the development time, and the film thickness before and after development at 400 mJ / cm ² . The ratio (development residual film ratio) and the minimum size of a line and space (L / S) pattern remaining without peeling as a measure of the adhesiveness after development are shown.

[0051]

[Table 1]

Further, after applying and drying each of the above varnish-like solutions on a silicon wafer, in an inert oven,
Heat treatment was performed at 350 ° C. for 2 hours in a nitrogen atmosphere to form a heat-cured film of polybenzoxazole. After the cured film is formed, the sample is treated with a pressure cooker (131 ° C., 3.0 atm) for 100 hours, and then subjected to a grid test (JIS K5400) so that 100 squares of 1 mm square are formed. Then, a cellophane tape was stuck from above and then peeled off, and the number of squares remaining on the substrate without adhering to the cellophane tape was counted to evaluate the water-resistant adhesiveness.

[0053]

As described above, according to the present invention, a novel alkoxysilane compound is provided as an adhesive suitable for a heat-resistant resin composition, and this is added to a heat-resistant photosensitive resin precursor composition. As a result, excellent adhesiveness to the substrate can be obtained in pattern formation during development, and a good fine pattern of a heat-resistant resin can be stably obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA04 AA14 AA18 AB16 AB17 AC01 AD01 BC13 BC42 CA00 CC03 CC06 FA17 4J011 PA47 PA97 PB40 PC02 PC05 QA17 QA18 QA23 QA34 QB16 RA10 SA06 SA21 SA31 SA36 SA41 SA51 SA01 SA01 AB34 AB38 BA50 DB36

Claims (2)

[Claims] 1. A heat-resistant resin precursor and an alkoxysilane compound represented by the following general formula (1): (R1 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; R2 is a divalent organic group having 1 to 20 carbon atoms;
Represents a divalent organic group having 1 to 10 carbon atoms. R4 and R5 represent an organic group having 1 to 10 carbon atoms, and m represents an integer of 0 to 2. X
Represents a divalent organic group containing a carbonyl group. A photosensitive resin composition containing a photopolymerization initiator, a compound having an unsaturated double bond, and a diluting solvent. 2. The photosensitive resin composition according to claim 1, wherein the alkoxysilane compound is represented by the following general formula (2). Embedded image