JP2001220443A - Polybenzoxazole precursor resin and photosensitive resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition exhibiting high sensitivity to (i) line ray even when having thick film thickness by using a resin composition exhibiting high transmittance in ultraviolet and visible-light regions without deteriorating excellent heat resistance and other various properties. SOLUTION: This polybenzoxazole precursor is characterized in that light transmittance of a film formed after coated therewith and dried is >=80%, at 365 nm wavelength per 10 μm thickness. The precursor is preferably composed of a polyamide represented by general formula (1) and 10-100 mol% of Y in general formula (1) is preferably composed of an aliphatic hydrocarbon having at least two or more carbon atoms. The photosensitive resin composition is obtained by using the precursor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polybenzoxazole precursor having high transparency to ultraviolet and visible light, and a photosensitive polybenzoxazole resin composition using the same. .

[0002]

2. Description of the Related Art Polyimide resin has excellent heat resistance to withstand the semiconductor process temperature, and is used as a passivation film in the semiconductor industry for reasons such as relaxation of stress, flattening of steps, and prevention of memory cell soft errors. It is used as a line shield layer and an interlayer insulating film. When used for these applications, it is necessary to perform pattern processing, and for this reason, photosensitive polyimide obtained by imparting photosensitivity to a polyimide resin has been widely put to practical use. In addition, polyimide resin has begun to be expected as an array electrode protective film, an insulating film, and even a liquid crystal alignment film in liquid crystal-related components, and this polyimide resin has low dielectric constant, low water absorption, ultraviolet light, and visible light region. High transparency is required. However, conventional polyimides have absorption in the short wavelength region of ultraviolet light and visible light, and have not reached practical use.

[0003] Also, with respect to photosensitive polyimide, the conventional product is usually used for g-ray exposure, and has good pattern workability for g-ray exposure. However, in the case of i-line exposure, the conventional product has a problem in that light does not penetrate to the bottom of the film when the film thickness is large because the polyimide itself as the base resin absorbs the i-line. Therefore, it has been difficult to perform fine pattern processing for i-line exposure.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide excellent heat resistance and other properties without impairing ultraviolet light, Another object of the present invention is to provide a photosensitive resin composition exhibiting a high transmittance in a visible light region. In particular, it is an object of the present invention to provide a photosensitive resin composition having high sensitivity to i-line even if the film thickness is large.

[0005]

According to the present invention, a film formed after coating and drying a polybenzoxazole precursor has a light transmittance at a wavelength of 365 nm of 8 μm / 10 μm.
It is a polybenzoxazole precursor characterized by being at least 0%. In a preferred embodiment, the polybenzoxazole precursor comprises a polyamide represented by the general formula (1), and in the general formula (1), 10 to 100 of Y
Molar% is a polybenzoxazole precursor composed of an aliphatic hydrocarbon having at least two or more carbon atoms, and more preferably, a polybenzoxazole precursor in which Z in the general formula (1) has the following structure And a photosensitive resin composition using the same.

[0006]

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[0007]

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[0008]

DETAILED DESCRIPTION OF THE INVENTION The polybenzoxazole precursor used in the present invention has a thickness of 10 μm.
The light transmittance at a wavelength of 365 nm of the film after pre-baking is 80
% Or more, and the polybenzoxazole precursor is made of a polyamide represented by the general formula (1). If the light transmittance at a wavelength of 365 nm of the prebaked film having a thickness of 10 μm is less than 80%, there is a problem that the sensitivity to i-line is deteriorated.

In the general formula (1), Y is at least 1
It is a divalent organic group containing both of at least one kind of aliphatic group and at least one kind of cyclic compound group, of which 10 to 100 mol% is a divalent organic group having an aliphatic group.
From the viewpoint of transparency to ultraviolet and visible light short wavelength regions,
Y is preferably an aliphatic divalent group. For that reason, by containing an aliphatic hydrocarbon in the polymer main chain, conjugation in the polymer can be suppressed, and as a result, ultraviolet,
And that the transmittance in the visible light short wavelength region is improved.

The inner aliphatic of Y in the general formula (1) is, for example,

[0011]

Embedded image Etc., but are not limited to these.

Among these, particularly preferred are:

[0013]

Embedded image It is more chosen. Y is one of these.
It may be composed of species or a copolymer composed of two or more species.

It is also possible to introduce a cyclic compound group into the polymer as a copolymer component other than the above as long as the transmittance in the ultraviolet and visible light short wavelength regions is not reduced. Preferred cyclic compound groups include

[0015]

Embedded image Etc., but are not limited to these.

When Y is composed of two or more kinds,
From the viewpoint of transmittance for short wavelengths of ultraviolet light and visible light, it is preferable to contain 10 to 100 mol% of the aliphatic hydrocarbon based on the whole Y. If it is less than 10 mol%, there is a problem that the transmittance for ultraviolet and visible light short wavelengths is reduced.

X in the above general formula (9) is a tetravalent cyclic compound group.

[0018]

Embedded image Etc., but are not limited to these.

Among these, particularly preferred are:

[0020]

Embedded image It is more chosen. X is one of these.
It may be composed of species or a copolymer composed of two or more species.

Z in the general formula (1) is a divalent cyclic compound group, for example, m-phenylenediamine, 1-isopropyl-2,4-phenylenediamine,
p-phenylenediamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-
Diaminodiphenylethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane,
4,4′-diaminodiphenyl sulfide, 3,3′-
Diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 3,
3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-
Diaminobenzanilide, benzidine, 3,3′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethoxybenzidine,
4,4′-diamino-p-terphenyl, 3,3′-diamino-p-terphenyl, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) Benzene, p-bis (2-methyl-4-aminopentyl)
Benzene, p-bis (1,1′-dimethyl-5-aminopentyl) benzene, 2,2-bis {4- (4-aminophenoxy) phenyl} propane, bis {4- (4-aminophenoxy) phenyl} Sulfone, bis 4- (3
-Aminophenoxy) phenyl} sulfone, 4,4'-
Bis (aminophenoxy) biphenyl, bis {4- (4
-Aminophenoxy) phenyl} ether, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 1,5-diaminonaphthalene, 2,6
-Diaminonaphthalene, 2,4-bis (β-amino-t
-Butyl) toluene, 2,4-diaminotoluene, m-
Xylene-2,5-diamine, p-xylene-2,5-
Diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino1,3,4-oxadiazole, 1,4-diaminocyclohexane, Piperazine,
Methylenediamine, ethylenediamine, propylenediamine, 2,2-dimethylpropylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3-methoxyhexamethylenediamine, heptamethylenediamine, 2, 5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylnonamethylenediamine, decamethylenediamine , 1,10-diamino-1,10-dimethyldecane, 2,11-diaminododecane, 1,12
-Diaminooctadecane, 2,12-diaminooctadecane, 2,17-diaminoicosane, diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-diamino-4,4'-dicarboxylic benzidine and the like However, the present invention is not limited to these.

Of these, from the viewpoint of transparency in the ultraviolet and visible light short wavelength regions, particularly preferred are:

[0023]

Embedded image It has the following structure. By including the above structure in the polymer main chain, conjugation in the polymer can be suppressed, and as a result, the transmittance in the ultraviolet and visible light short wavelength regions is improved.

The molar fraction a in the general formula (1) is from 70 to 10 because the amide moiety forms an oxazole ring by a ring-closing reaction at 300 to 400 ° C. and has heat resistance.
It is preferably 0 mol%.

E is used for modifying the amino terminal group of the hydroxypolyamide to improve the storage stability.

E can represent the following:

[0027]

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Specific examples are maleic anhydride, norbornene dicarboxylic anhydride and 4-vinyl-benzoic acid chloride. The advantage of using derivatives of unsaturated carboxylic acids is that an additional networking reaction occurs during the sintering process.

The photosensitive polybenzoxazole resin composition of the present invention mainly comprises a polybenzoxazole precursor represented by the general formula (1) and a photosensitive diazoquinone compound.

The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is disclosed in US Pat. Nos. 2,772,972 and 2,797, 21
No. 3,669,658.

For example, the following may be mentioned.

[0032]

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[0033]

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Among these, the following are particularly preferred.

[0035]

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The compounding amount of the photosensitive diazidoquinone compound (B) to the polyamide (A) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide. If the compounding amount is less than 1 part by weight, the patterning property of the resin is poor. Conversely, if it exceeds 100 parts by weight, the tensile elongation of the film is significantly reduced.

A dihydropyridine derivative can be added to the positive photosensitive resin composition of the present invention, if necessary, to enhance the photosensitive characteristics. Examples of the dihydropyridine derivative include 2,6-dimethyl-3,5-diacetyl-
4- (2'-nitrophenyl) -1,4-dihydropyridine, 4- (2'-nitrophenyl) -2,6-dimethyl-3,5-dicarbethoxy-1,4-dihydropyridine, 4- (2 ', 4'-Dinitrophenyl) -2,6
-Dimethyl-3,5-carbomethoxy-1,4-dihydropyridine and the like.

If necessary, additives such as a leveling agent and a silane coupling agent can be added to the photosensitive polybenzoxazole resin composition of the present invention.

In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-
Dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene Glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate and the like may be used alone or in combination.

The method of using the photosensitive polybenzoxazole resin composition of the present invention is as follows.
For example, it is applied to a silicon wafer, ceramic, aluminum substrate or the like. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. Next, 60-130
After pre-baking at ℃ and drying the coating film, a desired pattern shape is irradiated with actinic radiation. X-rays, electron beams,
Ultraviolet light, visible light, etc. can be used,
Those having a wavelength of m are preferred. Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia;
Primary amines such as ethylamine and n-propylamine;
Secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An aqueous solution of an alkali such as a quaternary ammonium salt or an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as alcohol such as methanol or ethanol or a surfactant thereto can be suitably used. As a developing method, a system such as spray, paddle, immersion, and ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinsing liquid.
Next, heat treatment is performed to form an oxazole ring, and a final pattern having high heat resistance is obtained.

Since the photosensitive polybenzoxazole resin composition of the present invention has a high light transmittance at the time of exposure, a good pattern can be obtained even with a thick film.

[0043]

[Example] <Synthesis of active ester as intermediate> 4-4 '
-Oxydibenzoic acid (hereinafter referred to as OBA) 2
58.23 g and 260.26 g of 1-hydroxybenzotriazole (hereinafter referred to as HBT) were added to anhydrous N-methyl-
Dissolve in 2170 g of 2-pyrrolidone (hereinafter referred to as NMP) and cool to 5 ° C. 412. Dicyclohexylcarbodiimide (hereinafter referred to as DCC) was added to 536 g of NMP in this solution.
The solution in which 66 g is dissolved is added dropwise over 1 hour while maintaining the temperature at 5 ° C. in the system. Further, 268 g of NMP is added, and the mixture is stirred and left at 25 ° C. for 20 hours. Next, the precipitate (dicyclohexylurea) of this reaction solution is filtered off and washed with 940 g of NMP. Next, 2400 distilled water was added to the filtrate while stirring.
g is added dropwise. The solid precipitated at this time is recovered, and the solid is stirred and washed with 3200 g of isopropyl alcohol for 1 hour. The washed solid is collected and dried under vacuum at 40 ° C. for 18 hours. The resulting active ester is hereinafter referred to as AE.

Example 1 124.0 g of adipic acid and 1
-Hydroxybenzotriazole (hereinafter referred to as HBT)
Dissolve 275.20 g in 1200 g NMP and cool to 10 ° C. To this solution was added 350.20 of dicyclohexylcarbodiimide (hereinafter referred to as DCC) in 456 g of NMP.
g, and the solution is maintained at 10 ° C. in the system and added dropwise over 1 hour. Further, 260 g of NMP was added, and the mixture was stirred and left at 25 ° C. for 20 hours. Next, 104.5 g of AE, 303.50 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 80.80 g of 1,3-bis (3-aminophenoxy) benzene (hereinafter referred to as APB).
And 135 g of NMP. After stirring at room temperature for 2 hours, the temperature in the system is raised to 75 ° C., and the mixture is further stirred at 75 ° C. for 18 hours. Next, 72.60 g of 5-norbornene-2-dicarboxylic anhydride was dissolved in 362 g of NMP, and
While maintaining the temperature at 0 ° C, the solution was charged, and the mixture was further stirred at 75 ° C for 3 hours. Next, the mixture is cooled to room temperature, dicyclohexylurea as a precipitate is filtered off, and the filtrate is poured into a mixed solution of isopropyl alcohol and distilled water while stirring. At this time, the precipitated solid is recovered and further washed with a mixed solution of isopropyl alcohol and distilled water. Collect the washed solids,
Dry at 40 ° C. for 48 hours under vacuum to obtain a polybenzoxazole precursor.

A resin obtained by dissolving 40.0 g of the obtained polybenzoxazole precursor in 60.0 g of γ-butyrolactone was applied to a quartz plate using a spin coater.
Dry on a hot plate at 120 ° C for 4 minutes to form a film with a thickness of 10μ.
m was obtained. The transmittance of this coating film was measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). The transmittance at a wavelength of 365 nm was 85%.

100 g of the above synthesized polybenzoxazole precursor, diazoquinone (Q
-1) After dissolving in 25 parts by weight and 200 parts by weight of γ-butyl lactone, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive polybenzoxazole resin composition.

Next, the photosensitive resin composition obtained above was applied on a silicon wafer by using a spin coater, and then prebaked at 120 ° C. for 4 minutes using a hot plate to form a film having a thickness of 12.5 μm. Obtained. This coating film was exposed through an i-line stepper exposure line NSR-2205i12C (manufactured by Nikon Corporation) through a mask having a test pattern. After exposure, development is performed by immersing in a developer of a 2.38% aqueous solution of tetraammonium hydroxide for 50 seconds, followed by rinsing with pure water for 30 seconds,
Got the pattern. The film thickness after development was 10.2 μm. Observing the obtained pattern with an optical microscope,
A good pattern was shown when the exposure amount was 500 mJ / cm ² .

Example 2 164.0 g of sebacic acid and H
Dissolve 262.90 g of BT in 1400 g of NMP and add
Cool down to To this solution was added DCC to 435 g of NMP.
The solution in which 34.50 g is dissolved is kept at 10 ° C. in the system and added dropwise over 1 hour. Further, 250 g of NMP is added, and the mixture is stirred and left at 25 ° C. for 20 hours. Next, 99.8 g of AE, 2, 2
270.60 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 92.60 g of APB and 925 g of NMP are introduced. After stirring at room temperature for 2 hours, the temperature in the system is raised to 75 ° C., and the mixture is further stirred at 75 ° C. for 18 hours. Next, 69.30 g of 5-norbornene-2-dicarboxylic anhydride was dissolved in 347 g of NMP, and the solution was dissolved at 75 ° C.
, And the mixture is left to stir at 75 ° C. for 3 hours. Next, the mixture is cooled to room temperature, dicyclohexylurea as a precipitate is filtered off, and the filtrate is poured into a mixed solution of isopropyl alcohol and distilled water while stirring. At this time, the precipitated solid is recovered and further washed with a mixed solution of isopropyl alcohol and distilled water. The washed solid is collected and dried under vacuum at 40 ° C. for 48 hours to obtain a polybenzoxazole precursor.

A resin obtained by dissolving 40.0 g of the obtained polybenzoxazole precursor in 60.0 g of γ-butyrolactone was applied to a quartz plate using a spin coater.
Dry on a hot plate at 120 ° C for 4 minutes to form a film with a thickness of 10μ.
m was obtained. The transmittance of this coating film was measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). The transmittance at a wavelength of 365 nm was 84%.

100 g of the above synthesized polybenzoxazole precursor, diazoquinone (Q
-1) After dissolving in 25 parts by weight and 200 parts by weight of γ-butyl lactone, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive polybenzoxazole resin composition.

Next, the photosensitive resin composition obtained above was applied on a silicon wafer using a spin coater, and then prebaked at 120 ° C. for 4 minutes using a hot plate to form a film having a thickness of 12.4 μm. Obtained. This coating film was exposed through an i-line stepper exposure line NSR-2205i12C (manufactured by Nikon Corporation) through a mask having a test pattern. After exposure, development is performed by immersing in a developer of a 2.38% aqueous solution of tetraammonium hydroxide for 50 seconds, followed by rinsing with pure water for 30 seconds,
Got the pattern. The film thickness after development was 10.0 μm. Observing the obtained pattern with an optical microscope,
A good pattern was shown when the exposure amount was 500 mJ / cm ² .

Example 3 157.8 g of adipic acid and H
Dissolve 350.20 g of BT in 1560 g of NMP and
Cool down to To this solution was added DCC to 580 g of NMP.
The solution in which 45.60 g was dissolved was kept at 10 ° C. in the system and added dropwise over 1 hour. Further, 290 g of NMP is added, and the mixture is stirred and left at 25 ° C. for 20 hours. Next, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 2
88.40 g, APB 98.60 g and NMP 430 g
Input. After stirring at room temperature for 2 hours, the temperature in the system is raised to 75 ° C., and the mixture is further stirred at 75 ° C. for 18 hours. Next 5
-Norbornene-2-dicarboxylic anhydride 73.9
0 g is dissolved in 370 g of NMP, added while maintaining the temperature at 75 ° C., and further stirred at 75 ° C. for 3 hours. Next, the mixture is cooled to room temperature, dicyclohexylurea as a precipitate is filtered off, and the filtrate is poured into a mixed solution of isopropyl alcohol and distilled water while stirring. At this time, the precipitated solid is recovered and further washed with a mixed solution of isopropyl alcohol and distilled water. The washed solid is collected and placed under vacuum at 40 ° C. 48
After drying for a time, a polybenzoxazole precursor is obtained.

A resin obtained by dissolving 40.0 g of the obtained polybenzoxazole precursor in 60.0 g of γ-butyrolactone was applied to a quartz plate using a spin coater.
Dry on a hot plate at 120 ° C for 4 minutes to form a film with a thickness of 10μ.
m was obtained. The transmittance of this coating film was measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). The transmittance at a wavelength of 365 nm was 98%.

100 g of the above synthesized polybenzoxazole precursor, diazoquinone (Q
-1) After dissolving in 25 parts by weight and 200 parts by weight of γ-butyl lactone, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive polybenzoxazole resin composition.

Next, the photosensitive resin composition obtained above was applied on a silicon wafer using a spin coater, and then prebaked at 120 ° C. for 4 minutes using a hot plate to form a film having a thickness of 12.4 μm. Obtained. This coating film was exposed through an i-line stepper exposure line NSR-2205i12C (manufactured by Nikon Corporation) through a mask having a test pattern. After the exposure, after developing by immersing in a developing solution of a 2.38% aqueous solution of tetraammonium hydroxide for 40 seconds, rinsing with pure water for 30 seconds,
Got the pattern. The film thickness after development was 9.8 μm.
Observation of the obtained pattern with an optical microscope revealed a favorable pattern with an exposure dose of 450 mJ / cm ² .

<Comparative Example 1> AE486.0 g, 2,2-
376.50 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 2450 g of NMP are introduced. After stirring at room temperature for 2 hours, the temperature in the system is raised to 75 ° C., and the mixture is further stirred at 75 ° C. for 18 hours. Next, 5-
Norbornene-2-dicarboxylic anhydride 67.50
g was dissolved in 340 g of NMP and charged while maintaining the temperature at 75 ° C., followed by stirring at 75 ° C. for 3 hours. Next, the mixture is cooled to room temperature, dicyclohexylurea as a precipitate is filtered off, and the filtrate is poured into a mixed solution of isopropyl alcohol and distilled water while stirring. At this time, the precipitated solid is recovered and further washed with a mixed solution of isopropyl alcohol and distilled water. The washed solid is collected and dried under vacuum at 40 ° C. for 48 hours to obtain a polybenzoxazole precursor.

A resin obtained by dissolving 40.0 g of the obtained polybenzoxazole precursor in 60.0 g of γ-butyrolactone was applied to a quartz plate using a spin coater.
Dry on a hot plate at 120 ° C for 4 minutes to form a film with a thickness of 10μ.
m was obtained. The transmittance of this coating film was measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). The transmittance at a wavelength of 365 nm was 48%.

100 g of the above synthesized polybenzoxazole precursor, diazoquinone (Q
-1) After dissolving in 25 parts by weight and 200 parts by weight of γ-butyl lactone, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive polybenzoxazole resin composition.

Next, the photosensitive resin composition obtained above was applied on a silicon wafer using a spin coater, and then prebaked at 120 ° C. for 4 minutes using a hot plate to form a film having a thickness of 12.4 μm. Obtained. This coating film was exposed through an i-line stepper exposure line NSR-2205i12C (manufactured by Nikon Corporation) through a mask having a test pattern. After exposure, the film is developed by immersing it in a developer of a 2.38% aqueous solution of tetraammonium hydroxide for 80 seconds, and then rinsed with pure water for 30 seconds,
Got the pattern. The film thickness after development was 9.9 μm.
Observation of the obtained pattern with an optical microscope showed a favorable pattern with an exposure dose of 600 mJ / cm ² .

<Comparative Example 2> 14.5 g of adipic acid and HB
Dissolve 32.20 g of T in 145 g of NMP and cool to 10 ° C. In this solution, DCC was added to 53 g of NMP in 41.00.
g, and the solution is maintained at 10 ° C. in the system and added dropwise over 1 hour. Further, 25 g of NMP was added, and the mixture was stirred and left at 25 ° C. for 20 hours. Next, AE440.1g, 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane (378.80 g) and NMP (2180 g) are charged.
After stirring at room temperature for 2 hours, the temperature in the system is raised to 75 ° C., and the mixture is further stirred at 75 ° C. for 18 hours. Next, 67.90 g of 5-norbornene-2-dicarboxylic anhydride was added to NMP.
Dissolve in 340 g, throw in while maintaining at 75 ° C., and stir at 75 ° C. for 3 hours. Then cool to room temperature,
The precipitate, dicyclohexylurea, is filtered off, and the filtrate is poured into a mixed solution of isopropyl alcohol and distilled water with stirring. The solid deposited at this time is recovered and further washed with a mixed solution of isopropyl alcohol and distilled water. Collecting the washed solid and drying under vacuum at 40 ° C. for 48 hours;
Obtain a polybenzoxazole precursor.

A resin obtained by dissolving 40.0 g of the obtained polybenzoxazole precursor in 60.0 g of γ-butyrolactone was applied to a quartz plate using a spin coater.
Dry on a hot plate at 120 ° C for 4 minutes to form a film with a thickness of 10μ.
m was obtained. The transmittance of this coating film was measured with an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). The transmittance at a wavelength of 365 nm was 54%.

100 g of the above synthesized polybenzoxazole precursor, diazoquinone (Q
-1) After dissolving in 25 parts by weight and 200 parts by weight of γ-butyl lactone, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive polybenzoxazole resin composition.

Next, the photosensitive resin composition obtained above was applied on a silicon wafer using a spin coater, and then prebaked at 120 ° C. for 4 minutes using a hot plate to form a film having a thickness of 12.5 μm. Obtained. This coating film was exposed through an i-line stepper exposure line NSR-2205i12C (manufactured by Nikon Corporation) through a mask having a test pattern. After exposure, development is performed by immersing in a developer of a 2.38% aqueous solution of tetraammonium hydroxide for 50 seconds, followed by rinsing with pure water for 30 seconds,
Got the pattern. The film thickness after development was 10.1 μm. Observing the obtained pattern with an optical microscope,
When the exposure amount was 580 mJ / cm ² , a good pattern was shown.

[0064]

The photosensitive polybenzoxazole resin composition of the present invention has excellent heat resistance and a high light transmittance in the ultraviolet and visible light regions of the polybenzoxazole precursor. And a good pattern can be obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naoshi Takeda 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. F-term (reference) 2H025 AA01 AA10 AB16 AB17 AC01 AD03 BE01 BJ00 CB26 CB41 CB45 FA29 4J002 CM021 EE056 EQ016 GP03 4J043 PA05 PA15 PA19 PB02 PB03 PB04 PB22 PC015 PC016 PC115 PC116 RA06 SA06 SA42 SA43 SA71 SA72 SB03 TA12 TB03 UA041 UA121 UA122 UA131 UA132 UA141 UA151 UA261 UB 012 UB UA UA UA UA UA UB281 UB282 UB301 UB302 UB311 UB401 VA011 VA012 VA021 VA022 VA031 VA041 VA042 VA051 VA052 VA061 VA062 VA081 VA082 VA092 VA102 XA16 XA19 ZB22

Claims (5)

[Claims] 1. coating a polybenzoxazole precursor,
A polybenzoxazole precursor, wherein a light transmittance at a wavelength of 365 nm of a film formed after drying is 80% or more per 10 μm of film thickness. 2. The polybenzoxazole precursor according to claim 1, comprising a polyamide represented by the general formula (1). Embedded image 3. In general formula (1), 10 to 1 of Y
The polybenzoxazole precursor according to claim 2, wherein 00 mol% comprises an aliphatic hydrocarbon having at least 2 or more carbon atoms. 4. The polybenzoxazole precursor according to claim 2, wherein Z in the general formula (1) has the following structure. Embedded image 5. A photosensitive polybenzoxazole resin composition comprising 100 parts by weight of the polybenzoxazole precursor according to claim 1 and 1 to 50 parts by weight of diazonaphthoquinone.