JPH06258834A - Heat-resistant photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain the heat-resistant photosensitive resin composition having both superior sensitivity and good film characteristics by incorporating a specified polyamidic ester and an acrylic compound having an amino group. CONSTITUTION:The heat-resistant photosensitive resin composition contains the acrylic compound having the amino group and the polyamidic ester represented by the formula in which X is a dimerizable or polymerizable group; R1 is a (2+p)-valent organic group; R2 is a tetra-valent organic group; p is 1 or 2; one of 2 carboxylic groups combining with R2 combines with an atom adjacent to the atom combining with one of the amido group and the other combines with the atom adjacent to the atom combining with the residual amid group. This polyamidic ester is obtained by a process like the manufacture conditions of general polyamidic acids from the starting materials of, for example, tetracarboxylic dianhydride, a diamine compound having a photodimerizable or photopolymerizable group, and the other diamine compounds.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyamic acid-based photosensitive resin composition.

[0002]

2. Description of the Related Art In recent years, heat-resistant organic materials such as polyimide resins have been used as insulating materials for semiconductors instead of conventional inorganic materials. On a semiconductor integrated circuit, it is necessary to form a hole for conduction called a via hole in an insulating film. Polyimide resin is generally applied on a substrate in the form of its precursor polyamic acid, which is processed by wet or dry etching using a photosensitive resist after heat curing or before heat curing to form a via hole. Form. However, if the precursor itself can be patterned by light, the process can be simplified and hydrazine as a dangerous polyimide etching agent can be omitted. Further, although fine pattern processing is required depending on the application, the former method cannot perform fine processing and the latter process is required. Under such circumstances, development of a polyimide precursor capable of forming a pattern by light (hereinafter referred to as a photosensitive polyimide) is underway.

For example, JP-B-55-30207 proposes a photosensitive polyimide in which a photosensitive group is introduced into a polyimide precursor through an ester bond, but it is difficult to increase the molecular weight and the photosensitive group is hard to volatilize during curing. For this reason, it has a defect that the film strength is poor. Also, JP-A-57-1689
Japanese Patent Laid-Open No. 42-42 proposes a photosensitive polyimide containing a mixture of a polyamic acid and an amine compound having a photopolymerizable or photocrosslinkable functional group as a main component, but has a drawback that the development latitude is narrow and the fine workability is poor. Have.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and provides a heat-resistant photosensitive resin composition having both excellent photosensitivity and good film characteristics. It is a thing.

[0005]

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

[Chemical 2] (In the formula, X represents a dimerizable or polymerizable group, R ₁ represents a (2 + p) -valent organic group, R ₂ represents a tetravalent organic group, and p represents an integer of 1 or 2. one of the two carboxyl groups bonded to R ₂ bonded to adjacent atoms of the atoms bonded to the amide group of one of the R _2, another carboxyl group adjacent to the atom of the atoms attached to the remainder of the amide group The present invention relates to a heat-resistant photosensitive resin composition containing a polyamic acid having a repeating unit represented by (bonded) and (B) an acrylic compound having an amino group.

In the general formula (I), X is

[Chemical 3] Etc., and in terms of ease of synthesis,

[Chemical 4] Is preferred. As R ₁ ,

[Chemical 5] Etc. As R ₂ ,

[Chemical 6] Etc.

The polyamic acid having a repeating unit represented by the general formula (I) (A) in the present invention is, for example, tetracarboxylic dianhydride, a diamine compound having a group which is polymerized or dimerized by light, and other It can be obtained by using a diamine compound as a material and in the same manner as the usual production conditions of polyamic acid.

The tetracarboxylic dianhydride used in the present invention includes, for example, pyromellitic dianhydride, 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3, 4,9,10-Perylenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, m-terphenyl-3,3 ", 4,4" -tetracarboxylic dianhydride, p -Terphenyl-3,
3 ", 4,4" -tetracarboxylic dianhydride, 4,4 '
-Oxydiphthalic acid dianhydride, 1,1,1,3,3,3
-Hexafluoro-2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3
3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,2
3-dicarboxyphenyl) propane dianhydride, 2,2
-Bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,
2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-
Hexafluoro-2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, the following general formula (II)

[Chemical 7] (R ₃ and R ₄ represent a monovalent hydrocarbon group, and may be the same or different, and s is an integer of 1 or more), such as an aromatic tetracarboxylic acid such as a tetracarboxylic anhydride. Examples thereof include anhydrides, and these can be used alone or in combination of two or more kinds.

Examples of diamine compounds having a group capable of being polymerized or dimerized by light include, for example, N- (2-methacryloyloxyethyl) -N '-[3- (4'-aminophenoxy) -6-aminophenyl. ] Urea, N- (2
-Methacryloyloxyethyl) -N '-[2- (4'
-Aminophenoxy) -5-aminophenyl] urea,
N- (2-methacryloyloxyethyl) -N'-
(2,5-Diaminophenyl) urea, N- (2-methacryloyloxyethyl) -N '-(3,5-diaminophenyl) urea, 4,4'-diamino-3,3'-bis (2-methacryloyl) Oxyethylcarbamoylamino) biphenyl, 3,3'-diamino-4,4'-bis (2-methacryloyloxyethylcarbamoylamino) biphenyl, 3,4'-diamino-4,3'-bis (2-methacryloyloxyethyl) Carbamoylamino) biphenyl, 4,4'-bis [3- (2-methacryloyloxyethylcarbamoylamino) -4-amino] phenoxybiphenyl, 1,4-bis [3- (2-
Methacryloyloxyethylcarbamoylamino) -4
-Amino] phenoxybenzene, 4,4'-bis [3-
(2-methacryloyloxyethylcarbamoylamino) -4-amino] phenoxybiphenyl ether and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

As other diamine compounds, for example, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 3,
3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4 '(or 3,4'-, 3,3'-,
2,4 '-)-diaminodiphenylmethane, 4,4'
(Or 3,4'-, 3,3'-, 2,4 '-)-diaminodiphenyl ether, 4,4' (or 3,4 '
-, 3,3'-, 2,4 '-)-diaminodiphenyl sulfone, 4,4' (or 3,4'-, 3,3'-,
2,4 '-)-diaminodiphenyl sulfide, 4,
4'-benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-di (4-aminophenoxy)
Phenyl sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy)
Benzene, 1,1,1,3,3,3-hexafluoro-
2,2-bis (4-aminophenonyl) propane, 2,
2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-
4,4'-diaminodiphenylmethane, 4,4'-di (3-aminophenoxy) phenyl sulfone, 3,3 '
-Diaminodiphenyl sulfone, 2,2'-bis (4-
Aromatic diamines such as aminophenyl) propane, 2,6
-Diaminopyridine, 2,4-diaminopyrimidine,
2,4-diamino-S-triazine, 2,7-diaminodibenzofuran, 2,7-diaminocarbazole, 3,
7-diaminophenothiazine, 2,5-diamino-1,
Heterocyclic diamines such as 3,4-thiadiazole, 2,4-diamino-6-phenyl-S-triazine, and
Trimethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,2-dimethylpropylenediamine, the following general formula (III)

[Chemical 8] (R ₅ and R ₆ represent a divalent hydrocarbon group, R ₇ and R ₈ represent a monovalent hydrocarbon group, and R ₅ , R ₆ , R ₇ and R ₈ may be the same or different. Of these, aliphatic diamines such as diaminopolysiloxane shown in (t is an integer of 1 or more) can be used, and these can be used alone or in combination of two or more kinds.

The polyamic acid in the present invention is produced in an aprotic polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc., except for special cases.

The acrylic compound having an amino group (B) used in the present invention is, for example, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N. -Diethylaminopropyl methacrylate, N, N-dimethylaminoethyl acrylate,
N, N-diethylaminoethyl acrylate, N, N-
Examples thereof include dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethylacrylamide, N, N-dimethylaminoethylacrylamide.

The amount of the acrylic compound having an amino group used is from 1 to 200% by weight based on (A) the polyamic acid having a repeating unit represented by the general formula (I) from the viewpoints of photosensitivity, heat resistant film strength and the like. %, Preferably 5
To 50% by weight is more preferable.

The photosensitive resin composition of the present invention may optionally contain the following (C) photopolymerization initiator. For example, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4′-bis (diethylamino)
Benzophenone, acetophenone, benzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-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-ethyl-N-
(P-chlorophenyl) glycine, N-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,3 ', 4,4'-tetra (t-
Butyl peroxycarbonyl) benzophenone, 3,
3'-Carbonylbis (7-diethylaminocoumarin)
Etc.

From the viewpoint of photosensitivity and film strength, the amount of the (C) photoinitiator used is 0.
It is preferably from 01 to 30% by weight, more preferably from 0.05 to 10% by weight.

The heat-resistant photosensitive resin composition of the present invention may optionally contain the following (D) addition-polymerizable compound. For example, diethylene glycol diacrylate,
Triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane tri Methacrylate, 1,4-butanediol diacrylate, 1,
6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-
Vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-
Examples thereof include methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide and N-methylolacrylamide.

The amount of the addition polymerizable compound (D) used is based on the polyamic acid having the repeating unit represented by the general formula (I) from the viewpoints of photosensitivity including solubility in a developing solution, film strength and the like. It is preferably 1 to 200% by weight.

The heat-resistant photosensitive resin composition of the present invention contains a radical polymerization inhibitor or a radical polymerization inhibitor such as p-methoxyphenol, hydroquinone, pyrogallol, phenothiazine and nitrosamines in order to enhance the stability during storage. May be.

The heat-resistant photosensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer, a metal substrate, a glass substrate or a ceramic substrate by a dipping method, a spray method, a screen printing method, a spin coating method or the like, and a solvent. By heating and drying most of the above, a coating film having no tackiness can be obtained. This coating film is exposed to actinic rays or actinic rays through a mask on which a desired pattern is drawn. Examples of the actinic ray or actinic ray to be applied include ultraviolet rays, far ultraviolet rays, visible light, electron rays, and X-rays. It is convenient to use UV light. After irradiation, the non-irradiated portion is dissolved and removed with an appropriate developing solution to obtain a desired relief pattern. As the developing solution, a good solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl-2-pyrrolidone or a mixed solvent thereof with a poor solvent such as a lower alcohol or an aromatic hydrocarbon, or A basic solution such as an aqueous solution of tetramethylammonium hydroxide or an aqueous solution of triethanolamine is used. After development, if necessary, rinse with water or a poor solvent and dry at about 100 ° C. to stabilize the pattern. At this stage, the polymer of this relief pattern is in the form of a precursor, and is 200 to 500 ° C., preferably 300 to 4 in order to make it heat resistant.
By heating at a temperature of 00 ° C. for several dozen minutes to several hours, a patterned high heat resistant polymer is formed. The chemical reaction in this case is considered to be as shown below. When the photosensitive component is in the ortho position of the amide bond, it is volatilized by thermal decomposition to form poly (imide-imidazopyrrolone).

[Chemical 9]

In this way, the photosensitive resin composition of the present invention can be converted into a buffer coat film for semiconductors, an interlayer insulating film of a multilayer wiring board and the like.

[0021]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 N- (2-methacryloyloxyethyl) was added to a 1 liter flask equipped with a stirrer, a thermometer and a dry air inlet tube.
-N '-[3- (4'-aminophenoxy) -6-aminophenyl] urea (42 g, 0.1 mol), 4,4'
-Diaminodiphenyl ether (20 g, 0.1 mol), N-methyl-2-pyrrolidone 300 g and 2,5
-Diphenyl-p-benzoquinone (50 mg) was added, the mixture was stirred and dissolved at room temperature under a dry air flow, and then cooled to 0 to 5 ° C.
Pyromellitic dianhydride (39.2 g, 0.
(2 mol) was added over 2 hours, and the mixture was stirred at the same temperature for 5 hours to obtain a viscous polyamic acid solution. Add this polymer solution to P-1
Call.

Example 1 10 g of the polyamic acid solution (P-1) obtained in Synthesis Example 1
3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (0.1 g), Michler's ketone (0.05 g) and N, N-dimethylaminoethyl methacrylate (1 g) were added and mixed with stirring. It was a photosensitive resin composition. After filtering with a filter, it was spin-coated on a silicon wafer. Then, it was heated on a hot plate at 100 ° C. for 200 seconds to dry the solvent to obtain a photosensitive coating film.
The film thickness after drying was 20 microns. Pattern exposure was performed on the coating film through a photomask with an ultra-high pressure mercury lamp. The exposure amount at this time was 500 mJ / cm ² . After this N-
Immersion development was performed with a mixed solution of methyl-2-pyrrolidone and methyl alcohol (volume ratio: 4/1). Further rinsed with isopropanol. This is 100 under nitrogen atmosphere.
The final cured film was heated at 15 ° C. for 15 minutes, at 200 ° C. for 20 minutes, and at 350 ° C. for 60 minutes. The final cured film thickness is 10 microns,
The minimum resolved through hole diameter was 10 microns.
Further, a cured film was obtained under the same curing conditions without separately performing pattern exposure and development treatment, the cured film was peeled from the substrate by hydrofluoric acid treatment, and film characteristics were evaluated. The evaluation results are shown in Table 1.

Comparative Example 1 A 500 ml separable flask was charged with 10.9 g of pyromellitic dianhydride, 16.1 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and N-methyl-2.
-Pyrrolidone 100.0 g, pyridine 15.8 g and 2
-Add 27.0 g of hydroxyethyl methacrylate,
Stir at room temperature for 20 hours. While cooling with ice, 75.0 g of an N-methyl-2-pyrrolidone solution containing 41.2 g of dicyclocarbodiimide was added dropwise over 10 minutes. Further, under ice cooling, 100.0 g of an N-methyl-2-pyrrolidone solution containing 20 g of 4,4′-diaminodiphenyl ether was added to 15
Dropped in minutes. After stirring at room temperature for another 4 hours, the mixture was poured into 5 liters of ethanol to generate a precipitate. After washing with an additional 2 liters of ethanol, 24 at 30 ° C
Allowed to dry for hours. This was dissolved in N-methyl-2-pyrrolidone to obtain a 35 wt% polymer solution. This polymer solution is called P-2. The photosensitive coating film was evaluated in the same manner as in the examples. As a result, the film thickness after curing is 1
A through hole of 10 micron could be opened at 0 micron.

[0024]

[Table 1]

[0025]

EFFECTS OF THE INVENTION The heat-resistant photosensitive resin composition of the present invention has excellent patterning processability and film properties.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 21/027 21/312 B 7352-4M

Claims (1)

[Claims] 1. (A) General formula (I): (In the formula, X represents a dimerizable or polymerizable group, R ₁ represents a (2 + p) -valent organic group, R ₂ represents a tetravalent organic group, and p represents an integer of 1 or 2. one of the two carboxyl groups bonded to R ₂ bonded to adjacent atoms of the atoms bonded to the amide group of one of the R _2, another carboxyl group adjacent to the atom of the atoms attached to the remainder of the amide group A photosensitive resin composition comprising a polyamic acid having a repeating unit represented by (bonding) and (B) an acrylic compound having an amino group.