JP2002122990A - Photosensitive polyimide precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive polyimide precursor composition excellent in stability, producible in a simple production process, forming a high resolution pattern and capable of giving a film excellent in strength and elongation characteristics after curing. SOLUTION: The photosensitive polyimide precursor composition contains (a) a polymer having a structural unit of formula (1) (where R1 is a tri-or tetravalent >=2C organic group; R2 is a divalent >=2C organic group; R3 is H, an alkali metal ion, an ammonium ion or at least one or 1-30C organic groups; and (n) is 1 or 2) and (b) a (meth)acrylate compound of formula (2) (where R4 is H, methyl or ethyl; R5 is a (m+n)-valent >=2C organic group; and (m) is an integer of >=2) having two or more hydroxyl groups in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a semiconductor device.
The present invention relates to a photosensitive polyimide precursor composition useful for producing electric and electronic materials such as a multilayer wiring board.

[0002]

2. Description of the Related Art Polyimide has excellent heat resistance, electrical properties, and mechanical properties.
It is widely used as an interlayer insulating film of a multilayer wiring board, a stress buffer coat, and the like. Further, since photosensitive polyimide itself has pattern processing properties, the process can be simplified as compared with the case where pattern processing is performed on ordinary non-photosensitive polyimide using a resist or the like.

The following is known as a negative photosensitive polyimide composition in which an exposed portion remains after development. (A) A composition obtained by carbonizing a polyamic acid with a carbon-carbon double bond capable of being dimerized or polymerized by actinic radiation, and an amino group or a quaternized salt thereof (for example, Japanese Patent Publication No. 59-52822). Compositions comprising a polyimide precursor having a carbon-carbon double bond group, a specific oxime compound and a sensitizer (for example, JP-A-61-118423, JP-A-6-118423)
However, in these methods, (a) has insufficient varnish stability, and (b) has a complicated production process and cure. There was a problem that the physical properties of the subsequent film were inferior.

[0004]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention has excellent stability and a simple manufacturing process.
An object of the present invention is to provide a photosensitive polyimide precursor composition capable of providing a high-resolution pattern and providing a film having excellent physical properties after curing.

[0005]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the polyimide precursor composition of the present invention is characterized by containing the following (a) and (b). (A) Polymer having a structural unit represented by general formula (1) (b) (meth) acrylate compound having two or more hydroxyl groups in a molecule represented by general formula (2)

[0006]

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(R ¹ represents a trivalent or tetravalent organic group having at least two or more carbon atoms, and R ² represents a divalent organic group having at least two or more carbon atoms.
³ is hydrogen, alkali metal ion, ammonium ion,
Alternatively, it represents at least one selected from organic groups having 1 to 30 carbon atoms. n is 1 or 2. )

[0008]

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(R ⁴ represents any one of hydrogen, a methyl group, and an ethyl group, and R ⁵ represents an (m + 1) -valent organic group having 2 or more carbon atoms, and m is an integer of 2 or more.)

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The object of the present invention is to provide a film which is excellent in stability, has a simple manufacturing process, can obtain a high-resolution pattern, and has excellent elongation characteristics after curing. The present inventors have intensively studied possible polyimide precursor compositions, and as a polyimide precursor composition comprising a polymer having a specific structural unit and a specific compound, they have sought to solve these problems at once.
That is, the present invention is a polyimide precursor composition including a specific polyimide precursor polymer and a (meth) acrylate compound having two or more hydroxyl groups in a molecule.

The polyimide precursor of the present invention has a structural unit represented by the following general formula (1), and has a polymer having an imide ring or other cyclic structure by heating or an appropriate catalyst (hereinafter referred to as “polyimide polymer”). ) Can be used.

[0012]

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(R ¹ represents a trivalent or tetravalent organic group having at least two or more carbon atoms, and R ² represents a divalent organic group having at least two or more carbon atoms.
³ is hydrogen, alkali metal ion, ammonium ion,
Alternatively, it represents at least one selected from organic groups having 1 to 30 carbon atoms. n is 1 or 2. In the general formula (1), R ¹ is a trivalent or tetravalent organic group having at least two or more carbon atoms, and contains an aromatic ring or an aromatic heterocyclic ring due to heat resistance of the polyimide polymer. And a tetravalent group having 6 to 30 carbon atoms is preferable. n is 1 or 2. From the viewpoint of the heat resistance of the polyimide polymer, n is preferably 2. Preferred specific examples of R ¹ include 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, 3,3 ′, 4,4 ′ −
Diphenylhexafluoropropanetetracarboxylic acid,
3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid,
Cyclopentanetetracarboxylic acid, 2,3 ', 3,4'
-Biphenyltetracarboxylic acid, 3,3 ', 4,4'-
Diphenylmethanetetracarboxylic acid, 3,3 ′, 4
4'-terphenyltetracarboxylic acid, 1,4,5,8
Residues such as, but not limited to, -naphthalenetetracarboxylic acid. From the viewpoint of the heat resistance of the polyimide-based polymer, a particularly preferred specific example is 3,
3 ', 4,4'-biphenyltetracarboxylic acid, 3,
3 ′, 4,4′-diphenylethertetracarboxylic acid, 3,3 ′, 4,4′-diphenylhexafluoropropanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′ , 4,4'-diphenylsulfonetetracarboxylic acid, pyromellitic acid,
2,3 ′, 3,4′-biphenyltetracarboxylic acid,
Residues such as 3,3 ', 4,4'-diphenylmethanetetracarboxylic acid, 3,3', 4,4'-terphenyltetracarboxylic acid and 1,4,5,8-naphthalenetetracarboxylic acid are exemplified. . The polyimide precursor in the present invention may have one type of R ¹ or a copolymer composed of two or more types.

In the above general formula (1), R ² is at least 2
It is a divalent organic group having at least two carbon atoms. In view of the heat resistance of the polyimide polymer, R ² is preferably a divalent group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R ² include paraphenylenediamine, metaphenylenediamine, methylparaphenylenediamine, methylmetaphenylenediamine, dimethylparaphenylenediamine, dimethylmetaphenylenediamine, trimethylparaphenylenediamine, trimethylmetaphenylenediamine, and tetramethyldiphenylenediamine. Methyl paraphenylenediamine, tetramethyl metaphenylenediamine, trifluoromethyl paraphenylenediamine, trifluoromethyl metaphenylenediamine, bis (trifluoromethyl) paraphenylenediamine, bis (trifluoromethyl) metaphenylenediamine, methoxyparaphenylenediamine, Methoxymetaphenylenediamine, trifluoromethoxyparaphenylenediamine, trifluoromethoxymetaphe Diamine, fluoroparaphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxy Carbonyl metaphenylenediamine, diaminodiphenylmethane, bis (aminomethylphenyl) methane,
Bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl)
Methane, bis (aminodiethylphenyl) methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (aminotrifluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (amino Dimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane Bis (aminochlorophenyl) hexafluoropropane, bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) Safluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bis (aminotrifluoromethylphenyl) sulfone, bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, Diaminodiphenyl ether, bis (aminomethylphenyl) ether, bis (aminotrifluoromethylphenyl) ether, bis (aminoethylphenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl)
Ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (Aminophenoxyphenyl) methane, bis (aminophenoxyphenyl) sulfone, 3,
5-diaminobenzoic acid methacryloyl ethyl ester,
3,5-diaminobenzoic acid acroyl ethyl ester,
Residues such as 2,4-diaminobenzoic acid methacryloyl ethyl ester, 2,4-diaminobenzoic acid acroylethyl ester, diaminobenzoic acid, dihydroxybenzidine, bis (amino-hydroxy-phenyl) hexafluoropropane, diaminophenol and the like; Examples include, but are not limited to, the residue of the hydrogenated compound.
In the polyimide precursor of the present invention, R ² may be composed of one of these, or may be a copolymer composed of two or more.

Further, in order to improve the adhesiveness of the polyimide-based polymer, it is possible to copolymerize an aliphatic group having a siloxane bond as R ² as long as the heat resistance is not reduced. A preferred specific example is bis (3
-Aminopropyl) tetramethyldisiloxane and the like, but are not limited thereto.

In the above general formula (1), R ³ is hydrogen, an alkali metal ion, an ammonium ion, or a compound having 1 carbon atom.
Represents at least one type of structure selected from organic groups of 30 to 30; As the organic group having 1 to 30 carbon atoms, an aliphatic organic group is preferable, and examples of the contained organic group include a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. It is not limited to these. R ³ may be a single species or a mixture of two or more species.

In order to improve the stability of the varnish,
In the general formula (1), 50% or more of R ³ has 1 to 5 carbon atoms.
Is preferred. Specific examples include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. The proportion of the hydrocarbon group having 1 to 5 carbon atoms in R ³ is preferably at least 60%, more preferably at least 80%.

The number average molecular weight of the polymer having the structural unit represented by the general formula (1) is preferably 5,000 to 50,000. If it is smaller than this range, a film having sufficient strength cannot be obtained, and if it is larger than this range, the solubility of the unexposed polymer during development becomes insufficient. A more preferred range for the number average molecular weight of the polymer is 10,000.
~ 30000.

The polyimide precursor in the present invention may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. . At that time, it is preferable that the content of the structural unit represented by the general formula (1) is 80% or more. The type and amount of the structural unit used for copolymerization or blending are preferably selected within a range that does not significantly impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

The polyimide precursor in the present invention is synthesized by various known methods. Particularly, when R ³ is hydrogen, it is preferable to synthesize the polyimide precursor by reacting a tetracarboxylic dianhydride with a diamine. I can say. It can be synthesized by the reaction of acid dianhydride and diisocyanate,
Care must be taken because the imidation rate of the polymer may increase. When R ³ is a hydrocarbon group, a preferred method is to add a dialkyl acetal of dimethylformamide to a polymer synthesized by reacting tetracarboxylic dianhydride with a diamine.

Examples of the polymerization solvent include a solvent containing N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide, etc.
Solvents containing butyrolactone as a main component, and cyclic ketone solvents such as cyclohexanone and cyclopentanone are preferably used.

In order to improve the in-plane uniformity at the time of spin coating, the solvent of the polyimide precursor in the present invention preferably contains a polymer-soluble low-boiling solvent such as cyclopentanone or cyclohexanone as a main component. In this case, N
-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, and the like. Once the precipitate is collected, it may be prepared by re-dissolving in a solvent containing the above-mentioned low-boiling-point solvent as a main component, or may be polymerized in a solvent containing a low-boiling-point solvent as a main component from the beginning.

Furthermore, when a solvent having a low boiling point such as cyclopentanone or cyclohexanone is used, the polyimide precursor composition preferably contains a surfactant.
Without the surfactant, the thickness unevenness of the coating film may increase. The amount of the surfactant to be added is preferably in the range of 1 to 10000 ppm, more preferably in the range of 100 to 6000 ppm, based on the polymer. If the amount is smaller than this amount, the surface active effect is not sufficient. If the amount is larger than this amount, care must be taken because the adhesion between the cured polyimide and the sealant or the upper wiring is reduced. As the type of surfactant, it is preferable to add a fluorine-based surfactant, an oxymethylene-based surfactant, and an acrylic-based surfactant.

The polyimide precursor composition of the present invention comprises, in addition to the polymer having the structural unit represented by the above general formula (1), two or more hydroxyl groups in the molecule represented by the following general formula (2) (Meth) acrylate compounds having the formula:

[0025]

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(R ⁴ represents any one of hydrogen, a methyl group and an ethyl group, and R ⁵ represents an (m + 1) -valent organic group having 2 or more carbon atoms. M is an integer of 2 or more.) The (meth) acrylate compound referred to in the formula (2) is a generic name of an acrylate compound or a methacrylate compound.

As a specific example of the general formula (2),
Glycerol monomethacrylate represented by the following formula (3) is preferably used, but is not limited thereto.

[0028]

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The content of the (meth) acrylate compound represented by the general formula (2) is preferably 50 to 400 mol%, more preferably 100 to 300 mol, based on the structural unit of the general formula (1). %. If it is smaller than this range, the film thickness retention rate after development decreases, the development speed decreases, and the resolution decreases.If it exceeds this range, the resolution decreases, the varnish gels, and the polyimide film after heat curing. Care must be taken since this will cause a decrease in elongation.

Such a (meth) acrylate compound needs to have two or more hydroxyl groups in the molecule. A (meth) acrylate compound having two or more hydroxyl groups in a molecule has a higher boiling point than a (meth) acrylate compound having no hydroxyl group or one hydroxyl group having the same molecular weight, and is volatilized during prebaking. Is unlikely to occur. Further, by having two or more hydroxyl groups, interaction with the polymer is possible at a plurality of sites. Due to these features, it is possible to provide a photosensitive polyimide precursor composition having a high sensitivity and a high residual film ratio, despite the simple method of mixing the polyimide precursor and the (meth) acrylate compound. .

In order to obtain higher sensitivity and higher resolution in the pattern after development, it is preferable to include a photoinitiator and a photosensitizer. These photoinitiators and photosensitizers can be used alone or in combination.

Examples of the photoinitiator include aromatic amines such as N-phenyldiethanolamine, N-phenylglycine, and Michler's ketone; cyclic oxime compounds represented by 3-phenyl-5-isoxazolone; and 1-phenylpropanedione-2. -(O-ethoxycarbonyl)
A chain oxime compound represented by an oxime, a benzophenone derivative such as benzophenone, methyl o-benzoylbenzoate, dibenzyl ketone and fluorenone, a thioxanthone derivative such as thioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone are preferably used. .

Examples of the sensitizer include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone; coumarin compounds such as 3,3'-carbonylbis (diethylaminocoumarin); and aromatic compounds such as benzanthrone and phenanthrenequinone. Preferred are those generally used for photocurable resins, such as ketones, and any other materials used as charge transfer agents for electrophotography.

The photoinitiator and the sensitizer are preferably added in an amount of 0.01 to 30% by weight, more preferably 0.1 to 20% by weight, based on the weight of the polymer. If the ratio is out of this range, the photosensitivity is lowered and the mechanical properties of the polymer are lowered.

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after the heat treatment and the support, an adhesion aid may be appropriately used.

Examples of the adhesion promoter include oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organic silicon compounds such as methacryloxypropyltrimethoxysilane, or aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate and aluminum tris (acetylacetonate) or titanium chelate compounds such as titanium bis (acetylacetonate) are preferable. Used.

Further, other additives may be used to improve adhesion to the substrate,
Sensitivity and heat resistance may be included in a range that does not significantly decrease.

Next, the method of using the composition of the present invention will be described. The composition of the present invention can be patterned by a known fine processing technique using actinic radiation.

First, the composition of the present invention is applied on a suitable substrate. As the material of the substrate, for example, metal, glass,
A semiconductor, a metal oxide insulating film, silicon nitride, or the like can be used, but is not limited thereto.

As a coating method, means such as spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating and the like are possible. The coating thickness can be adjusted by the coating means, the solid content concentration of the composition, and the viscosity, but is preferably 0.1 to 150 μm.
It is applied so as to be within the range.

Next, the substrate coated with the polyimide precursor is dried to obtain a polyimide precursor composition film. Drying is
Use an oven, hot plate, infrared ray, etc.
It is preferably carried out in the range of ~ 150 ° C, 40 ~ 100 ° C
It is more preferable to carry out within the range. Drying time is 10 seconds ~
Preferably, it is performed for several hours. If the film has already been dried immediately after the application, the drying step can be omitted.

Next, exposure is performed using a mask having a desired pattern. Exposure amount is 50-1000mJ
/ Cm ² is preferred. A particularly preferred range is 100
６００600 mJ / cm ² . By using an appropriate sensitizer, exposure can be performed using an exposure machine such as an i-line stepper, a g-line stepper, a mask aligner, and a mirror projection aligner.

The resolution of the pattern at the time of development is improved,
When the allowable range of the developing conditions is increased, a step of performing a baking process before the development may be adopted. The temperature is preferably in the range of 30 to 150 ° C.,
The range of 00 ° C is more preferable. The time is preferably from 10 seconds to several hours. If the ratio is out of this range, the reaction may not proceed or all the regions may not be dissolved.

Subsequently, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. An appropriate developer can be selected in accordance with the structure of the polyimide precursor, but an aqueous alkali solution such as ammonia, tetramethylammonium hydroxide, or diethanolamine can be preferably used. Also,
Cyclopentanone and cyclohexanone which are main solvents of the present composition, and N-methyl-2-pyrrolidone and N-acetyl-2- which are general solvents for dissolving the polyimide precursor
Pyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, γ-butyrolactone, or the like alone, or methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene A mixed solution with glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl acetate and the like can also be preferably used.

The development can be carried out by irradiating the above-mentioned developing solution on the surface of the coating film as it is or in the form of mist, immersing in the developing solution, or applying ultrasonic waves while immersing. .

Next, it is preferable to wash the relief pattern formed by development using water or an organic solvent. When washing with an organic solvent as the washing liquid, methanol, ethanol,
Isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3
-Ethoxypropionate, 2-heptanone, ethyl acetate and the like are preferably used.

The polymer of the relief pattern obtained by the above treatment is a precursor of a polyimide-based polymer having heat resistance, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. The heat treatment is preferably performed at a temperature of 135 to 500 ° C.
More preferably, the reaction is performed at 0 to 450 ° C. Such heat treatment is preferably performed stepwise or continuously while increasing the temperature.

[0048]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples. In the synthesis examples and examples, abbreviations of polyimide raw materials are used in the following manner.

4,4'-DAE: 4,4'-diaminodiphenyl ether p-BAPS: bis [4- (4-aminophenoxy) phenyl] sulfone HFBAPP: bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane HFHA: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane SiDA: bis (3-aminopropyl) tetramethyldisiloxane PMDA: pyromellitic anhydride BTDA: 3, 3 ', 4, 4 '-Benzophenonetetracarboxylic dianhydride ODPA: 3,3', 4,4'-diphenylethertetracarboxylic dianhydride DMFDMA: dimethylformamide dimethyl acetal GLM: glycerol monomethacrylate HEMA: 2-hydroxyethyl methacrylate NPG: - phenylglycine NNAP: 1- nitroso-2-naphthol CP: cyclopentanone NMP: N-methyl-2-pyrrolidone Synthesis Example 1 Dry air under a stream 4 in four-necked 1 liter flask,
9.61 g (0.048 mol) of 4'-DAE, p-BA
PS 17.3 g (0.04 mol), SiDA 1.24 g
(0.005 mol) was dissolved in 102.5 g of CP at 40 ° C. Thereafter, 6.54 g (0.03 mol) of PMDA, 9.67 g (0.03 mol) of BTDA, and ODPA
12.41 g (0.04 mol) and 30 g of CP were added, and 5
The reaction was performed at 0 ° C. for 3 hours. This was designated as varnish A.

Synthesis Examples 2 to 7 Diamine and acid dianhydride were used in the amounts shown in Table 1 to obtain Synthesis Examples 1 to 7.
A composition was prepared in the same manner as described above. Each varnish was designated Varnish B to Varnish G.

[0051]

[Table 1]

Synthesis Example 8 Synthesis Example 1 except that NMP was used instead of CP as the solvent
A composition was prepared in the same manner as described above. After cooling to room temperature, DM
29.78 g of FDMA was added and the mixture was stirred at 40 ° C. for 2 hours. This solution was put into 1 L of pure water to precipitate a polymer, and the polymer was collected by filtration, washed three times with pure water, and then dried with a vacuum dryer at 80 ° C. for 8 hours. 30 g of the polymer powder thus obtained was dissolved in 70 g of CP. This was designated as varnish H.

Synthesis Example 9 Synthesis Example 2 except that NMP was used instead of CP as a solvent
A varnish B was prepared in the same manner as described above. Varnish B, DMFDMA
And a composition was prepared in the same manner as in Synthesis Example 8, and this was designated as varnish I.

Synthesis Example 10 Synthesis Example 3 except that NMP was used instead of CP as the solvent
A varnish C was prepared in the same manner as described above. Varnish C, DMFDMA
Was used to prepare a composition in the same manner as in Synthesis Example 8, and this was designated as Varnish J.

Synthesis Example 11 Synthesis Example 4 except that NMP was used instead of CP as a solvent
A varnish D was prepared in the same manner as described above. Varnish D, DMFDMA
Was used to prepare a composition in the same manner as in Synthesis Example 8, and this was designated as Varnish K.

Synthesis Example 12 Synthesis Example 5 except that NMP was used instead of CP as a solvent
A varnish E was prepared in the same manner as described above. Varnish E, DMFDMA
Was used to prepare a composition in the same manner as in Synthesis Example 8, and this was designated as Varnish L.

Synthesis Example 13 Synthesis Example 6 except that NMP was used instead of CP as a solvent
A varnish F was prepared in the same manner as described above. Varnish F, DMFDMA
Was used to prepare a composition in the same manner as in Synthesis Example 8, and this was designated as Varnish M.

Synthesis Example 14 Synthesis Example 7 except that NMP was used instead of CP as a solvent
A varnish G was prepared in the same manner as described above. Varnish G, DMFDMA
Was used to prepare a composition in the same manner as in Synthesis Example 8, and this was designated as Varnish N.

Example 1 1.5 g of GLM, 0.09 g of NPG, and 10 g of varnish A
NNAP 0.002 g, acrylic surfactant (manufactured by Kusumoto Kasei Co., Ltd .: "Dispalon" LC-951) 0.02 g
Was added and stirred to obtain a photosensitive varnish.

A varnish is spin-coated on a 4-inch silicon wafer, and then baked on a hot plate at 70 ° C. for 3 minutes (apparatus: SKW-6 manufactured by Dainippon Screen Mfg. Co., Ltd.).
36) At this time, the coating rotation was adjusted so that the film thickness after baking was about 8 μm.

Next, a mask aligner (Canon P
(LA-501F). The exposure dose measured by i-line was 300 mJ / cm ² . After exposure, the film was developed with a developing solution of cyclohexanone / cyclopentanone = 1/1 (weight ratio), then rinsed with propylene glycol monomethyl ether acetate, and dried.

As a result of observing the pattern after development, the film thickness retention ratio of the exposed portion was 92%, and a 10 μm pattern was resolved. There was no problem with the pattern shape.

Example 2 A photosensitive varnish was prepared in the same manner as in Example 1 except that varnish B was used instead of varnish A. Pattern processing was performed in the same manner as in Example 1 using a 4-inch silicon wafer. As a result of observing the pattern after development, the film thickness retention ratio of the exposed portion was 87%, and a 10 μm pattern was resolved. There was no problem with the pattern shape.

Examples 3 to 14 Photosensitive varnishes were prepared in the same manner as in Example 1 except that the varnishes used were changed from C to N as shown in Table 2. Pattern processing was performed in the same manner as in Example 1 using a 4-inch silicon wafer. Table 2 shows the evaluation results. In each case, a high-resolution pattern was obtained, and there was no problem in the pattern shape.

COMPARATIVE EXAMPLE 1 0.09 g of NPG and 0.09 g of NNAP were added to 10 g of varnish A.
01 g, acrylic surfactant (manufactured by Kusumoto Kasei Co., Ltd .: "
0.02 g of Dispalon "LC-951) was added and stirred to obtain a photosensitive varnish.

The varnish was subjected to pattern processing in the same manner as in Example 1. However, after development, the entire film was dissolved, and a pattern could not be formed.

Comparative Example 2 To 10 g of varnish A, 1.50 g of HEMA and 0.0
9 g, NNAP 0.002 g, acrylic surfactant (manufactured by Kusumoto Chemicals, Ltd .: "Dispalon" LC-951)
0.02 g was added and stirred to obtain a photosensitive varnish.

The varnish was subjected to pattern processing in the same manner as in Example 1. However, dissolution of the unexposed portion was extremely slow, and cracks were observed after development. Further, when the baking condition was set to 80 ° C., no pattern was formed at all.

[0069]

[Table 2]

[0070]

According to the present invention, a photosensitive polyimide precursor having excellent stability, a simple manufacturing process, a high resolution pattern, and a film having excellent elongation characteristics after curing can be obtained. A composition can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/312 H01L 21/312 BD DF term (Reference) 2H025 AA10 AA13 AB15 AB16 AC01 AD01 BC34 CB25 CB55 FA29 4J011 AC04 QA03 QA34 RA06 RA10 RA12 RA17 SA07 SA17 SA21 SA22 SA31 SA34 SA41 SA42 SA63 SA64 SA65 SA78 SA80 SA82 TA04 UA01 VA01 WA01 4J026 AB34 AC33 BA30 BB01 DB06 DB24 DB36 EA06 FA05 GA07 5F058 AA10 AC02 AC07 AF04 AG01 AG09 A09H09

Claims (4)

[Claims] 1. A photosensitive polyimide precursor composition comprising the following (a) and (b): (A) Polymer having a structural unit represented by general formula (1) (b) (meth) acrylate compound having two or more hydroxyl groups in a molecule represented by general formula (2) (R ¹ represents a trivalent or tetravalent organic group having at least 2 or more carbon atoms, R ² represents a divalent organic group having at least 2 or more carbon atoms. R ³ represents hydrogen, alkali Represents at least one selected from a metal ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms, and n is 1 or 2. (R ⁴ represents any of hydrogen, a methyl group and an ethyl group,
R ⁵ represents a (m + 1) -valent organic group having 2 or more carbon atoms. m
Is an integer of 2 or more. ) 2. The photosensitive polyimide precursor composition according to claim 1, wherein the polymer having the structural unit represented by the general formula (1) has a number average molecular weight of 5,000 to 50,000. 3. The polyimide precursor composition according to claim 2, wherein in formula (1), at least 50% of R ³ is a hydrocarbon group having 1 to 5 carbon atoms. 4. A polymer having a structural unit represented by the general formula (1), wherein the (meth) acrylic compound represented by the general formula (2) is contained in an amount of 50 to 400 mol%. The polyimide precursor composition according to claim 1.