JP2003316002A - Photosensitive resin composition, method for producing pattern using the same and electronic parts - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive polyimide precursor composition excellent in photosensitive characteristics, having high sensitivity, giving a pattern of a good shape even under low light exposure, ensuring a high rate of a residual film after development, low temperature curability and a low shrinkage percentage of a coating film after heat curing and giving a cured film excellent in cured film properties and to provide a method for producing a pattern using the composition, capable of shortening a production process and capable of reducing production cost. <P>SOLUTION: The photosensitive polyimide precursor composition comprises a polyimide precursor, an addition-polymerizable compound and a photoinitiator, wherein a diamine component and an acid anhydride component forming the polyimide precursor have an aromatic ring, the diamine component has a non- straight chain flexuous structure and the addition-polymerizable compound has a molecular weight of ≤350. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high adhesiveness, a small shrinkage rate of a coating film after heat curing, a sharp taper angle of a pattern and suitable for low temperature curing. A photosensitive resin composition suitable for an interlayer insulating film of a wiring board, a method for producing a pattern using this composition, and an electronic component, and in particular, a negative photosensitive resin composition which becomes a heat-resistant polyimide polymer by heat treatment. The present invention relates to an object and pattern manufacturing method and an electronic component.

[0002]

2. Description of the Related Art A polyimide or its precursor, which also has a photo-patterning property by itself, is called a photosensitive polyimide and is used for a surface protective film of a semiconductor. Several methods of imparting photosensitivity are known for photosensitive polyimide. A representative one is Japanese Examined Japanese Patent Publication No.55-4
A mixture of a polyamic acid as an ester of hydroxyacrylate as proposed in Japanese Patent No. 1422 and a polyamic acid as proposed in JP-A No. 54-145794 and an amino acrylate. It is known to introduce a photosensitive group by a salt bond. Since polyamic acid itself is rigid in these materials, there is a drawback that the film state formed by spin coating or the like has lower sensitivity than conventional ultraviolet curable paints and dry film resists. To improve this, sensitivity can be increased by adding an oxime ester compound, an arylglycine compound, or the like. However, on the other hand, when it is cured at a low temperature, there are drawbacks such as insufficient cured film properties and reduced adhesion. In addition, there is a problem that the shape of the polyimide pattern after heat-curing is significantly changed.

[0003]

The present invention has been made to solve the above-mentioned problems, and is a useful composition capable of forming a cured product of a heat-resistant photosensitive resin which satisfies the above-mentioned required characteristics. It is an object to provide an object and a pattern forming method using the object. A first object of the present invention is that it can be cured at a low temperature, has excellent photosensitivity, high sensitivity, a pattern of a good shape can be obtained even at a low exposure amount, a residual film rate after development is high, and a cured film property is also high. An object of the present invention is to provide a photosensitive resin composition which can obtain an excellent cured film and has a small coating film shrinkage after being cured by heating. A second object of the present invention is that it can be cured at a low temperature, has excellent photosensitivity, high sensitivity, a pattern of a good shape can be obtained even at a low exposure dose, a high residual film rate after development, and a high heat-curable pattern after heat curing. It is an object of the present invention to provide a method for producing a pattern, which can obtain a cured film having a small coating film shrinkage rate and excellent cured film characteristics, can further shorten the manufacturing process, and can reduce the manufacturing cost. A third object of the present invention is to provide an electronic component having excellent reliability in addition to the above objects.

[0004]

The present invention provides (A) general formula (I)

[0005]

[Chemical 2]

(In the formula, X is a group containing a tetravalent aromatic ring, Y is a group containing a divalent aromatic ring, R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and X is And at least one of Y has one aromatic ring), a polyimide precursor having a repeating unit represented by the formula, an addition polymerizable compound having a molecular weight of 350 or less, and (C) a photosensitive resin containing a photoinitiator. It relates to a composition. In the present invention, the polyimide precursor is a polyamic acid unsaturated ester having a (meth) acryloxyalkyloxy group as R ¹ and R ² , and the esterification rate is 50 to 80 mol%. Resin composition.

In the present invention, the step of applying the above-mentioned photosensitive resin composition on a supporting substrate to form a polyimide precursor film, the polyimide precursor film is formed through a photomask having a predetermined pattern. The present invention relates to a method for producing a pattern, which comprises a step of irradiating with actinic rays for exposure and then dissolving and removing an unexposed portion with an organic solvent or a basic aqueous solution to obtain a desired relief pattern. Further, the present invention is
The present invention relates to an electronic component having a polyimide film obtained by imidizing the pattern obtained by the above manufacturing method as a surface protective film or an interlayer insulating film.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Polyimide acid, polyamic acid ester, polyamic acid amide and the like are available as types of the polyimide precursor having the repeating unit represented by the general formula (I) used in the present invention. Although not particularly limited, R1 and R2 in the general formula (I) are preferably a polyimide precursor in which a monovalent organic group having a photopolymerizable carbon-carbon unsaturated double bond is used. Examples of such a polyimide precursor include a polyamic acid unsaturated ester having a structure in which a compound having a photopolymerizable carbon-carbon unsaturated double bond is covalently bonded to a polyamic acid as a side chain, a polyamic acid unsaturated amide, and a polyamic acid. Preferred examples include those having a structure in which an amine compound having a carbon-carbon double bond is mixed with and a carbon-carbon double bond is introduced by an ionic bond between a carboxyl group and an amino group.

The polyamic acid unsaturated ester is prepared by mixing a tetracarboxylic dianhydride and a hydroxy group-containing compound having an unsaturated group and reacting them to prepare a half ester of tetracarboxylic acid, and then acid chloride with thionyl chloride. Can be synthesized by a method of reacting with a diamine, an acid chloride method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent, a method of using a carbodiimide condensing agent, an isoimide method, and the like.

When the carbon-carbon unsaturated double bond is introduced by the ester bond, the amount of the compound having the carbon-carbon double bond introduced is determined by the solubility in the developing solution, photocurability,
From the viewpoint of heat resistance and the like, it is preferably 20 to 100% with respect to the carboxyl group of the polyamic acid, and 30 to
It is more preferably 90% and even more preferably 50-80%.

Examples of the compound having a carbon-carbon unsaturated double bond include 2-hydroxyethyl acrylate,
3-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, pentaerythritol diacrylate monostearate, pentaerythritol triacrylate, caprolactone 2- (methacryloxy) ethyl Examples thereof include esters and dicaprolactone 2- (methacryloyloxy) ethyl ester.

The weight average molecular weight of the polyimide precursor is preferably 3,000 to 200,000, more preferably 5,000 to 100,000. The molecular weight can be measured by a gel permeation chromatography method. In the present invention, the above (A) polyimide precursor has an aromatic ring in either or both of Y (generally a residue of a diamine component) and X (generally a residue of an acid anhydride component) of the general formula (I). Use one that has one. Examples of the diamine component include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,4-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid and 3,5-
Diaminochlorobenzene, 5-nitro-m-phenylenediamine, 4-chloro-m-phenylenediamine, 4,
6-dimethyl-m-phenylenediamine, 2,4-diaminomesitylene, 3,5-diaminoacetanilide,
Examples thereof include aromatic diamines such as 3,5-diaminobenzonitrile, 2,4-diaminopyridine, p-xylylenediamine, m-xylylenediamine, and o-xylylenediamine, but are not limited thereto. . Among them, m-phenylenediamine, 5-nitro-m-phenylenediamine and 4,6-dimethyl-m-phenylenediamine are preferable. These are used alone or in combination of two or more.

The diamine component of the (A) polyimide precursor may contain other diamine. For example, 4,4'-diaminodiphenyl ether, 4,4 '
-Diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, 4,4'-
Diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,3'-dimethyl-4,4'-
Diaminobiphenyl, 3,3'-dihydroxy-4,4 '
-Diaminobiphenyl and the like, but not limited thereto. When using these, it is preferable to use 1 to 90 mol% with respect to the total amine component. These diamines are used alone or in combination of two or more. In addition, as a diamine, the following general formula (II) is used to improve adhesiveness.

[0014]

[Chemical 3]

(In the formula, R ³ and R ⁴ represent a divalent hydrocarbon group, which may be the same or different, and R ⁵ and R ⁶ represent a monovalent hydrocarbon group, which may be the same or different. Alternatively, a diamine such as diaminopolysiloxane represented by the formula (t is an integer of 1 or more) can be used. Examples of R ³ and R ⁴ include an alkylene group such as a methylene group, an ethylene group and a propylene group, an arylene group such as a phenylene group, and a bonding group thereof. Examples of R ⁵ and R ⁶ include a methyl group and an ethyl group. And an aryl group such as a phenyl group, and a bonding group thereof. When these are used, 1 to the total amine component is used.
It is preferable to use 30 mol%. These diamines are used alone or in combination of two or more.

The acid anhydride used for producing the (A) polyimide precursor is not particularly limited, but examples thereof include pyromellitic dianhydride and benzene 1,2,3,4-tetracarboxylic dianhydride. Thing, 1,4-dimethoxy-2,3
5,6-benzenetetracarboxylic dianhydride, 1,4-
Trimethylsilyl-2,3,5,6-benzenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-cyclohexene Examples thereof include, but are not limited to, -1,2-dicarboxylic acid dianhydride. Moreover, in using these, they are used individually or in combination of 2 or more types.

Other acid anhydrides may be used as the acid anhydride component of the (A) polyimide precursor. For example, oxydiphthalic dianhydride, 3,3 ′,
4,4'-benzophenone tetracarboxylic dianhydride,
2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride 1,2,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, Cyclopentane-1,
2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride and the like, It is not limited to these. Of these, oxydiphthalic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are preferable. Moreover, in using these, they are used individually or in combination of 2 or more types.

As the addition polymerizable compound (B), 350
A compound having the following molecular weight is preferable, and a compound obtained by condensing a polyhydric alcohol and an α, β-unsaturated carboxylic acid, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol. Dimethacrylate, neopentyl glycol dimethacrylate, butylethylpropane diol methacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, butylethyl propanediol diacrylate,
Examples thereof include 1,6-hexanediol diacrylate, but are not limited thereto. These may be used alone or in combination of two or more.

The content of the component (B) is preferably 1 to 200 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polyimide precursor. If the amount used is less than 1 part by weight, the photosensitive properties including the solubility in the developer tend to be poor, and if it exceeds 200 parts by weight, the mechanical properties of the film tend to be poor.

The photoinitiator is not particularly limited, but examples thereof include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4-bis (diethylamino). Benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2
-Methyl- [4- (methylthio) phenyl] -2-morpholino 1-propanone, benzyl, diphenyl disulfide, phenanthrenequinone, 2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6
-Bis (p-diethylaminobenzal) -4-methyl-4-azacyclohexanone, N-ethyl-N- (p-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyiminopropan-1-one , 3,3,4,4-Tetra (t-butylperoxycarbonyl) benzophenone, 3,3-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis- [2,6-difluoro-3- (Pyryl-1-yl) phenyl] titanium, hexaarylbiimidazole compounds and the like are mentioned, but not limited to these. Also, these may be used alone or in 2
You may use it in combination of 2 or more types.

The content of the component (C) is preferably 1 to 30 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the polyimide precursor. The heat-resistant photosensitive resin composition of the present invention may contain a sensitizer, if necessary. Examples of the sensitizer include 7-
N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin, 3,3′-carbonylbis (7-N, N-diethylamino) coumarin, 3,3′-
Carbonylbis (7-N, N-dimethoxy) coumarin,
3-thienylcarbonyl-7-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N, N-methoxycoumarin, 3- (4'-methoxybenzoyl) coumarin, 3,3'-carbonylbis-5 , 7- (dimethoxy) coumarin, benzalacetophenone, 4′-N, N-dimethylaminobenzalacetophenone, 4′-acetaminobenzal-4-methoxyacetophenone, dimethylaminobenzophenone, diethylaminobenzophenone, 4,4′-bis Examples thereof include (N-ethyl, N-methyl) benzophenone and the like, but are not limited thereto. Also, the content of these is
0.05-2 with respect to 100 parts by weight of the polyimide precursor
The amount is preferably 0 part by weight, more preferably 0.1 to 10 parts by weight.

The heat-resistant photosensitive resin composition of the present invention may further contain other additives such as a plasticizer and an adhesion promoter.

The pattern manufacturing method of the present invention uses the heat-resistant photosensitive resin composition of the present invention to form a polyimide film of a cured product of the composition by photolithography. In the pattern manufacturing method of the present invention, first, a coating film made of the heat-resistant photosensitive resin composition of the present invention is formed on the surface of a supporting substrate. In the pattern manufacturing method of the present invention, the surface of the supporting substrate may be previously treated with an adhesion aid in order to improve the adhesiveness between the film or the polyimide coating after heat curing and the supporting substrate.

The coating film made of the photosensitive polyimide precursor composition is formed, for example, by forming a varnish film of the photosensitive polyimide precursor composition and then drying it. The pattern manufacturing method of the present invention is particularly suitable for forming by drying at low temperature, for example, suitable for forming at 300 ° C., and further suitable for forming at 250 ° C. The formation of the varnish film is performed by means appropriately selected from means such as spin coating using a spinner, dipping, spray printing, and screen printing according to the viscosity of the varnish. The film thickness of the coating film can be adjusted by the coating conditions, the solid content concentration of the composition, and the like. Further, by peeling the coating film previously formed on the support substrate from the support and pasting a sheet made of the polyimide precursor composition on the surface of the support substrate,
You may form the above-mentioned film.

Next, this coating is irradiated with light (ultraviolet rays or the like) through a photomask having a predetermined pattern, and then the unexposed portion is dissolved and removed by an organic solvent or a basic aqueous solution,
Obtain the desired relief pattern.

Examples of the organic solvent include acetone, methyl ethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, ethylene glycol monomethyl ether, ethylene glycol. Monoethyl ether, xylene, tetrahydrofuran, dioxane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, hexyl acetate, methyl cellosolve, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene acetate Glycol mono-n-butyl ether, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfo Sid, sulfolane, cyclohexanol, cyclohexanone, cyclohexane oxime,
Cyclohexane, 1,4-cyclohexanedimethanol, cyclohexyl acetate, cyclopentanol,
Examples thereof include cyclopentanone, cyclopentanone oxime, cyclopentane, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

The basic aqueous solution is usually a solution in which a basic compound is dissolved in water. The concentration of the basic compound is preferably 0.1 to 50% by weight, more preferably 0.1 to 30% by weight because of the influence on the supporting substrate and the like. In order to improve the solubility of the polyimide precursor, methanol, ethanol, propanol, isopropanol, butanol, N-methyl-2-pyrrolidone,
It may further contain a water-soluble organic solvent such as N, N-dimethylformamide or N, N-dimethylacetamide. Examples of the basic compound include alkali metal, alkaline earth metal or ammonium ion hydroxides or carbonates, and amine compounds.

In the obtained pattern, a part of the polyimide precursor of the present invention is usually imidized. By heating this pattern, a stable and highly heat-resistant polyimide pattern can be obtained. The heating temperature at this time is 13
The temperature is preferably 0 to 500 ° C., and 150 to 350 ° C.
Is more preferable. This heating temperature is 130 ℃
When it is less than 500 ° C, the mechanical properties and thermal properties of the polyimide film tend to deteriorate, and when it exceeds 500 ° C, the mechanical properties and thermal properties of the polyimide film tend to deteriorate.

The heating time at this time is 0.01 to 10
The time is preferably set, and more preferably 0.05 to 5 hours. If this heating time is less than 0.01 hours, the mechanical properties and thermal properties of the polyimide film will tend to deteriorate, and if it exceeds 10 hours, the mechanical properties and thermal properties of the polyimide film will tend to be inferior.

As described above, the photosensitive resin composition of the present invention is
It can be used as a surface protective film for semiconductors, an interlayer insulating film of a multilayer wiring board, and the like. The surface protective film using the photosensitive resin composition of the present invention has excellent adhesiveness to SiN, a sealant, etc., and therefore, a semiconductor device using the surface protective film obtained from the photosensitive resin composition of the present invention Is extremely reliable. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed by using the composition, and can have various structures.

[0031]

The present invention will be described below with reference to examples, but the present invention is not limited thereto. A method using N, N′-dihydrocarbyl-substituted carbodiimide as an isoimidizing agent is shown in the following synthesis examples, but trifluoroacetic anhydride may be used instead.

(Synthesis Example 1) 50 equipped with a dry nitrogen introducing tube
In a 0 ml four-necked flask, 8.7200 g (0.0400 mol) of pyromellitic dianhydride and 12.4080 g (0.040) of 4,4′-oxydiphthalic dianhydride.
0 mol) and dried N-methylpyrrolidone 100 ml
Was added and stirred, and to this solution was added 2.6000 g (0.0200 mol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C. and stirred for 1 hour, and then cooled to room temperature, 2.3358 g (0.0216 mol) of m-phenylenediamine and 5.4502 g (0.0504mo of p-phenylenediamine).
1) and 120 ml of dry N-methylpyrrolidone were added dropwise over 1 hour with stirring at room temperature and stirred overnight.

Then, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes while stirring at room temperature. Further, 2-hydroxyethyl methacrylate 31.2340 g (0.2400
mol) was added, and the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, and stirred overnight.

The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was adjusted to 2.0.
L was added slowly to the ion-exchanged water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion-exchanged water, washed with methanol and filtered by suction filtration,
A solid was obtained. The obtained solid is dried in a vacuum dryer until the water content at room temperature is 1.0% by weight or less,
A powdery solid was obtained.

(Synthesis Example 2) 50 equipped with a dry nitrogen introducing tube
Into a 0 ml four-necked flask, 24.8160 g (0.0800 mol) of 4,4′-oxydiphthalic dianhydride and 100 ml of dried N-methylpyrrolidone were added and stirred, and 2-hydroxyethyl methacrylate 2. 6000 g (0.0200 mol) was added. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C. and stirred for 1 hour, then cooled to room temperature, and 3,2862 g (0.0216 mol) of 2,4-diaminobenzoic acid and 5.4502 g of p-phenylenediamine ( 0.0504 mol) and 120 ml of dry N-methylpyrrolidone were added dropwise over 1 hour with stirring at room temperature, and the mixture was stirred overnight. Then, N, N-dicyclohexylcarbodiimide 26.8
200 g (0.1300 mol) and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes with stirring at room temperature. Furthermore, 31.2340 g (0.2400 mol) of 2-hydroxyethyl methacrylate was added,
After stirring at 50 ° C. for 5 hours, the mixture was cooled to room temperature and stirred overnight.

The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was adjusted to 2.0.
L was added slowly to the ion-exchanged water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion-exchanged water, washed with methanol and filtered by suction filtration,
A solid was obtained. The obtained solid is dried in a vacuum dryer until the water content at room temperature is 1.0% by weight or less,
A powdery solid was obtained.

(Synthesis Example 3) 50 equipped with a dry nitrogen introducing tube
Into a 0 ml four-necked flask, 24.8160 g (0.0800 mol) of 4,4′-oxydiphthalic dianhydride and 100 ml of dried N-methylpyrrolidone were added and stirred, and 2-hydroxyethyl methacrylate 2. 6000 g (0.0200 mol) was added. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C. and stirred for 1 hour, then cooled to room temperature, and 2.9160 g (0.0216mo) of 4,6-dimethyl-m-phenylenediamine.
l), p-phenylenediamine 5.4502 g (0.0
504 mol) and dried N-methylpyrrolidone 120 m
1 was added dropwise with stirring at room temperature over 1 hour and stirred overnight. Then, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes while stirring at room temperature. Further, 2-hydroxyethyl methacrylate 31.2340 g (0.2400
mol) was added, and the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, and stirred overnight.

The reaction mixture was diluted with 100 ml of acetone, and the filtrate obtained by removing unnecessary substances by suction filtration was adjusted to 2.0.
L was added slowly to the ion-exchanged water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion-exchanged water, washed with methanol and filtered by suction filtration,
A solid was obtained. The obtained solid is dried in a vacuum dryer until the water content at room temperature is 1.0% by weight or less,
A powdery solid was obtained.

(Synthesis Example 4) 50 equipped with a dry nitrogen introducing tube
In a 0 ml four-necked flask, 8.7200 g (0.0400 mol) of pyromellitic dianhydride and 12.4080 g (0.040) of 4,4′-oxydiphthalic dianhydride.
0 mol) and dried N-methylpyrrolidone 100 ml
Was added and stirred, and to this solution was added 2.6000 g (0.0200 mol) of 2-hydroxyethyl methacrylate. The solution was stirred at room temperature for 1 hour, further heated to 40 ° C. and stirred for 1 hour, then cooled to room temperature, 2.3358 g (0.0216 mol) of m-phenylenediamine, 4,
4'-diaminodiphenyl ether 10.0800 g
(0.0504 mol) and 120 ml of dry N-methylpyrrolidone were added dropwise with stirring at room temperature over 1 hour, and the mixture was stirred overnight.

Then, 26.8200 g (0.1300 mol) of N, N-dicyclohexylcarbodiimide and 100 ml of dry N-methylpyrrolidone were added dropwise over 30 minutes while stirring at room temperature. Further, 2-hydroxyethyl methacrylate 31.2340 g (0.2400
mol) was added, and the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, and stirred overnight.

The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was adjusted to 2.0.
L was added slowly to the ion-exchanged water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion-exchanged water, washed with methanol and filtered by suction filtration,
A solid was obtained. The obtained solid is dried in a vacuum dryer until the water content at room temperature is 1.0% by weight or less,
A powdery solid was obtained.

(Synthesis Example 5) 50 equipped with a dry nitrogen introducing tube
In a 0 ml four-necked flask, 23.5200 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (0.
0800 mol) and dried N-methylpyrrolidone 10
2 ml of 2-hydroxyethyl methacrylate (2.600Og (0.0200mo) was added to this solution and stirred.
l) was added. The solution was stirred at room temperature for 1 hour, then an additional 40
After heating to ℃ and stirring for 1 hour, it was cooled to room temperature and 2.3358 g (0.0216mo) of m-phenylenediamine.
l), 4,4'-diaminodiphenyl ether 10.0
800 g (0.0504 mol) and 120 ml of dry N-methylpyrrolidone were added dropwise at room temperature with stirring over 1 hour, and the mixture was stirred overnight. Then, 26.8200 g of N, N-dicyclohexylcarbodiimide (0.13
00 mol) and 100 ml of dry N-methylpyrrolidone were added dropwise with stirring at room temperature over 30 minutes. 2-hydroxyethyl methacrylate 31.2340
g (0.2400 mol) was added, and the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, and stirred overnight.

The reaction mixture was diluted with 100 ml of acetone, and the filtrate from which unnecessary substances were removed by suction filtration was adjusted to 2.0.
L was added slowly to the ion-exchanged water with vigorous stirring to obtain a precipitate. The deposited precipitate was further washed with ion-exchanged water, washed with methanol and filtered by suction filtration,
A solid was obtained. The obtained solid is dried in a vacuum dryer until the water content at room temperature is 1.0% by weight or less,
A powdery solid was obtained.

(Example 1) In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 35.0 g of the powder of the photosensitive polymer obtained in Synthesis Example 1 and 38. After dissolving 0 g and P-methoxyphenol 0.1 g with stirring, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.
A photosensitizer of 0 g and 0.2 g of ethyl Michler's ketone and 7.0 g of triethylene glycol diacrylate as an addition-polymerizable compound were added and dissolved with stirring overnight at room temperature, followed by filtration with a filter to obtain a photosensitive resin composition solution. This solution is spin-coated on a silicon wafer and then dried to 20 μm.
After forming a coating film of m, it was exposed with an i-line stepper FPA3000iW (manufactured by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. At an exposure dose of 300 mJ / cm 2, a good relief pattern without peeling was obtained. The residual film rate after development at this exposure amount was 95%. Also, the wafer after development is 250 ° C.
When heated for 2 hours, the film exhibited excellent cured film properties and adhesion, and the shrinkage rate of the coating film after thermosetting was 23%.

(Example 2) In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 35.0 g of the powder of the photosensitive polymer obtained in Synthesis Example 2 and 38. After dissolving 0 g and P-methoxyphenol 0.1 g with stirring, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.
0 g and 0.2 g of ethyl Michler's ketone and 7.0 g of 1,6-hexanediol diacrylate as an addition-polymerizable compound were added and dissolved with stirring overnight at room temperature, and filtered to obtain a photosensitive resin composition solution. Obtained. The solution is spin coated on a silicon wafer and then dried to 20
After forming a coating film having a thickness of μm, the film was exposed with an i-line stepper FPA3000iW (manufactured by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. A good relief pattern without peeling was obtained at an exposure dose of 350 mJ / cm 2. The residual film rate after development at this exposure amount was 93%. Also, the wafer after development is 250 ° C.
When heated for 2 hours, the film exhibited excellent cured film properties and adhesion, and the shrinkage rate of the coating film after thermosetting was 25%.

(Example 3) In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a nitrogen introducing tube, 35.0 g of the powder of the photosensitive polymer obtained in Synthesis Example 3 and 38. After dissolving 0 g and P-methoxyphenol 0.1 g with stirring, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.
0 g of ethyl Michler's ketone and 0.2 g of ethyl Michler's ketone and 7.0 g of triethylene glycol dimethacrylate as an addition-polymerizable compound were added and dissolved with stirring overnight at room temperature, followed by filtration with a filter to obtain a photosensitive resin composition solution. The solution is spin coated on a silicon wafer and then dried to 20
After forming a coating film having a thickness of μm, the film was exposed with an i-line stepper FPA3000iW (manufactured by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. A good relief pattern without peeling was obtained at an exposure dose of 400 mJ / cm 2. The residual film rate after development at this exposure amount was 91%. Also, the wafer after development is 250 ° C.
When heated for 2 hours, the film exhibited excellent cured film properties and adhesion, and the shrinkage rate of the coating film after thermosetting was 23%.

(Example 4) In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 35.0 g of the powder of the photosensitive polymer obtained in Synthesis Example 4 and 38. After dissolving 0 g and P-methoxyphenol 0.1 g with stirring, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 2.0 g, 2-mercaptobenzoxazole 1.
A photosensitizer of 0 g and 0.2 g of ethyl Michler's ketone and 7.0 g of triethylene glycol diacrylate as an addition-polymerizable compound were added and dissolved with stirring overnight at room temperature, followed by filtration with a filter to obtain a photosensitive resin composition solution. This solution is spin-coated on a silicon wafer and then dried to 20 μm.
After forming a coating film of m, it was exposed with an i-line stepper FPA3000iW (manufactured by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol. A good relief pattern without peeling was obtained at an exposure dose of 350 mJ / cm 2. The residual film rate after development at this exposure amount was 93%. Also, the wafer after development is 250 ° C.
When heated for 2 hours, the film exhibited excellent cured film properties and adhesion, and the shrinkage rate of the coating film after thermosetting was 27%.

(Example 5) In a 100 ml four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 35.0 g of the powder of the photosensitive polymer obtained in Synthesis Example 5 and 38. of dry N-methylpyrrolidone. After stirring and dissolving 0 g and P-methoxyphenol 0.1 g, 2.0 g of 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2-mercaptobenzoxazole 1.
0 g and Michler's ketone 0.2 g as a photosensitizer and 7.0 g of 1,6-hexanediol diacrylate as an addition-polymerizable compound were added and dissolved with stirring overnight at room temperature, and then filtered through a filter to obtain a photosensitive resin composition solution. . This solution was spin-coated on a silicon wafer and then dried to 20 μm.
After forming the coating film of No. 1, exposed by an i-line stepper FPA3000iw (manufactured by Canon Inc.) through a pattern mask, developed using a mixed solution of N-methylpyrrolidone and methanol, and rinsed with ethanol, A good relief pattern without peeling was obtained at an exposure dose of 350 mJ / cm 2. The residual film rate after development at this exposure amount was 92%. When the wafer after development was heated at 250 ° C. for 2 hours, it exhibited excellent cured film characteristics and adhesion, and the shrinkage rate of the coating film after thermal curing was 25%.

Comparative Example 1 Instead of m-phenylenediamine and p-phenylenediamine used in Synthesis Example 1,
The same procedure as in Example 1 was carried out using a photosensitive polymer powder obtained in the same manner as in Synthesis Example 1 except that 4,4′-diaminobiphenyl was used and pyromellitic dianhydride was not used as the acid component. However, although a relief pattern was obtained after development, the sensitivity of the i-line stepper was low and it was not practical.

(Comparative Example 2) A treatment was conducted in the same manner as in Example 2 except that dipentaerythritol hexaacrylate was used instead of the addition-polymerizable compound 1,6-hexanediol diacrylate used in Example 2. Although a relief pattern was obtained after development, the cured film properties after heat treatment were inferior.

(Comparative Example 3) When the same treatment as in Example 3 was carried out without using the addition-polymerizable compound triethylene glycol diacrylate used in Example 3, the sensitivity became low and the pattern swelled after development, resulting in a satisfactory pattern. Was not obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takeharu Motobu             Hitachi, Ichiba, Ibaraki Prefecture             Sei DuPont Micro Systems Co., Ltd. Yama             Inside the Saki Development Center (72) Inventor Toshiaki Itabashi             Hitachi, Ichiba, Ibaraki Prefecture             Sei DuPont Micro Systems Co., Ltd. Yama             Inside the Saki Development Center F term (reference) 2H025 AA01 AA10 AB16 AB17 AC01                       AD01 BC14 BC32 BC42 BC69                       CA01 CA20 CA27 CA28 FA03                       FA15 FA29                 5F058 AA08 AC02 AC07 AF04 AG01                       AH02 AH03

Claims (4)

[Claims] 1. A compound represented by the general formula (I): (In the formula, X is a group containing a tetravalent aromatic ring, Y is a group containing a divalent aromatic ring, R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and X and Y A heat-resistant photosensitive resin composition comprising a polyimide precursor having a repeating unit represented by at least one having one aromatic ring), an addition polymerizable compound having a molecular weight of 350 or less, and (C) a photoinitiator. 2. A polyimide precursor is a polyamic acid unsaturated ester having a (meth) acryloxyalkyloxy group as R ¹ and R ² , and having an esterification ratio of 5
The photosensitive resin composition according to claim 1, which is 0 to 80 mol%. 3. A step of applying the photosensitive resin composition according to claim 1 on a supporting substrate to form a polyimide precursor film, wherein the polyimide precursor is passed through a photomask having a predetermined pattern. A method for producing a pattern, which comprises the steps of irradiating with actinic rays for exposure and then dissolving and removing the unexposed portion with an organic solvent or a basic aqueous solution to obtain a desired relief pattern. 4. An electronic component comprising a polyimide film obtained by imidizing the pattern obtained by the manufacturing method according to claim 3 as a surface protective film or an interlayer insulating film.