JP2002040655A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is developable (etchable) with an aqueous alkali solution, without impairing its superior heat resistance, mechanical strength and electric insulating property peculiar to a polyimide and giving an image that is clear even down to minute parts. SOLUTION: The photosensitive resin composition contains a polyamic acid derivative (I) having a structural unit of formula (1) (where A is a tetravalent organic group; B is a group of formula (2); and R1 and R2 are each a monovalent organic group or hydroxyl, but at least one of R1 and R2 is an organic group having one or more hydroxyl groups bonding to an aromatic ring), a compound (II) which generates an acid, when irradiated with radiation and a compound (III) capable of crosslinking the polyamic acid derivative under the action of the acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming a pattern of a polyimide film used as an interlayer insulating film, a protective film and the like in a wiring portion of a semiconductor element or a high-density mounting substrate.

[0002]

2. Description of the Related Art Polyimide has high heat resistance, mechanical strength,
It has features such as chemical resistance, dimensional stability, flame retardancy, and electrical insulation. For this reason, polyimide is widely used in the field of electric and electronic equipment and the like, and particularly in the field where heat resistance and electric insulation are required, the field of use and the quantitative expansion are expected in the future.

In recent years, in the field of electric and electronics, polyimide has been used as a surface protection film for semiconductor elements and high-density mounting substrates, an interlayer insulating film, and the like. These films are usually required in the form of various relief patterns, and in order to form such patterns, it has been considered particularly desirable to form the patterns photolithographically by local irradiation with high energy radiation. Was.

[0004] However, polyimide is insoluble in organic solvents that have been widely used in the past, and is not suitable for such photolithographic applications. Therefore, a technique has been developed in which a radiation-sensitive group (for example, an acrylic group) is introduced into a carboxylic acid group of a polyamic acid, which is a precursor of a polyimide soluble in a general-purpose organic solvent, through an ester bond or the like, thereby imparting photosensitivity. Was. However, in this method, when the ring is thermally closed (formation of an imide ring) after the image is formed, the image is distorted or the film is reduced.

Therefore, a technique of solubilizing polyimide, which was generally insoluble in a solvent, in a general-purpose solvent and imparting photosensitivity has been studied. As a technique for solubilizing polyimide in a general-purpose organic solvent, for example, a technique of introducing a side chain group such as an alkyl group, a fluoroalkyl group, or an aromatic group into a raw material monomer has been developed.

As a technique for imparting photosensitivity to the solvent-soluble polyimide, a photosensitive polyimide containing an alkyl group and a benzophenone group has been developed. Tokuhei 5
The polyimides disclosed in JP-A-6956 or JP-A-5-53834 are soluble in general-purpose organic solvents and have both photosensitivity.

[0007] A polyimide having an unsaturated bond in a side chain is also disclosed. For example, T. Naka
no et al., 2nd International Co.
nreference on Polyimides, 1
63, Oct. 24-Nov. 1, 1985
In this paper, a diamine monomer having an unsaturated bond introduced by an amide bond was developed, and it was reported that a polyimide obtained therefrom has photosensitivity. However, these diamines have an amide bond or an ester bond in a side chain group and thus have a problem in hygroscopicity.
Limited to high boiling solvents such as -methyl-2-pyrrolidone.

The polymers obtained from the diamine compounds shown in these prior arts are all soluble in general-purpose organic solvents, but are insoluble in aqueous alkaline solutions widely used in photoresist technology. . If it is soluble in an aqueous alkaline solution, its application is expected to expand. New diamine compounds and polyimides that improve this point have been developed. Ueda et al. Macromol
ecules 1996, 29, 6427,
It has been found that a polyimide containing a phenolic hydroxyl group is soluble in an aqueous alkaline solution and has photosensitivity. However, this diamine compound contains only one phenolic hydroxyl group per diamine molecule. In order to further improve solubility and photosensitivity, it is necessary to increase the number of phenolic hydroxyl groups in the repeating structural unit.

Japanese Patent Application Laid-Open No. 6-161102 discloses a method in which a compound having an amino group, an amide group, a urethane group and the like is mixed with a polyamic acid, the exposure is controlled in the presence of a photoinitiator, and heating is performed. JP-A-5-5995 describes a method of mixing quinonediazide with a salt of a polyamic acid and an amine compound having a phenolic hydroxyl group, and JP-A-5-5995 describes a method of mixing a base generator such as nifedipine with polyamic acid. . Those based on these polyamic acids show relatively good developability,
It is difficult to obtain a difference in solubility between the exposed part and the unexposed part, and the film loss of the pattern is large. It is hard to say that the light sensitivity is high enough.

A mixture of a dibenzoquinone compound and a polybenzoxazole precursor (Japanese Patent Publication No. 1-46862), a mixture of a polyamic acid and a phenol moiety introduced through an ester bond (Japanese Patent Application Laid-Open No. 4-218051), etc. And those in which a phenolic hydroxyl group is introduced instead of a carboxylic acid, are known. However, there are problems such as insufficient developability and photosensitivity, and separation of the resin from the substrate.

For the purpose of improving such developability and adhesion,
Mixtures of polyamic acids having a siloxane moiety in the polymer skeleton (JP-A-4-31861 and JP-A-4-46345) have also been studied. Is insufficient. On the other hand, by irradiating excitation light such as UV and the resin portion having introduced a specific protecting group to the carboxyl group of the polyimide precursor,
There has been proposed a chemical photosensitive composition (JP-A-4-120171) in which an acidic compound is blended.
However, this is because a protecting group such as a tetrahydropyranyl group or 1
-When an ethoxyethyl group, a trimethylsilyl group, or the like is used as a protecting group, the sensitivity is good, but since these protecting groups are easily removed, there is a problem of storage stability in a solution state, and a heat treatment after exposure (hereinafter referred to as “heat treatment”). Pattern shape (resolution) depending on the standing time until reaching PEB) or PEB temperature
It is not practically sufficient, for example, because it greatly affects the sensitivity and sensitivity.

Further, a methyl group or an ethyl group as a protecting group,
When a propyl group, a butyl group, a benzyl group, or the like is used, storage stability in a solution is improved, but after the acid is generated by irradiation with excitation light, elimination of the protecting group does not sufficiently occur even after the PEB step, It is not a practical material.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition which can be developed with an aqueous alkali solution and has excellent photosensitivity and resolution.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to develop a novel photosensitive resin composition that solves the above-mentioned problems, and as a result, completed the present invention.

That is, the present invention relates to the general formula (1)

[0016]

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Wherein A is a tetravalent organic group, B is a group shown below,

[0018]

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R1 and R2 each represent a monovalent organic group or a hydroxyl group, and at least one of R1 and R2 represents an organic group having at least one hydroxyl group bonded to an aromatic ring. Contains a derivative (I), a compound (II) that generates an acid upon irradiation, and a compound (III) that can crosslink a polyimide acid derivative having a structural unit represented by the general formula (1) by the action of an acid. A photosensitive resin composition characterized by the general formula (1)

[0020]

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Wherein A is a tetravalent organic group, B is a group shown below,

[0022]

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R1 and R2 each represent a monovalent organic group or a hydroxyl group, and at least one of R1 and R2 represents an organic group having at least one hydroxyl group bonded to an aromatic ring. Derivatives and general formula (2)

[0024]

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(Wherein B represents a group equivalent to the formula (1),
Represents a tetravalent organic group, D may be the same as or different from A) and a mixture (I) with a polyamic acid having a structural unit represented by the formula (I):
A photosensitive resin composition comprising: (I) a compound (III) capable of crosslinking a polyimide acid derivative having a structural unit represented by the general formula (1) by the action of an acid; , General formula (1)

[0026]

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(Wherein A is a tetravalent organic group, B is a group shown below,

[0028]

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R1 and R2 each represent a monovalent organic group or a hydroxyl group, and at least one of R1 and R2 represents an organic group having at least one hydroxyl group bonded to an aromatic ring.

[0030]

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(Wherein B represents a group equivalent to the formula (1),
Represents a tetravalent organic group, D may be the same as or different from A), a polyamic acid derivative (I) having a copolymer structure containing a structural unit represented by the following formula: II) a compound (III) capable of crosslinking a polyamic acid derivative having a structural unit represented by the general formula (1) by the action of an acid. Furthermore, the polyamic acid derivative (I) is
The photosensitive resin composition contains 00 parts by weight, 0.5 to 20 parts by weight of the compound (II), and 3 to 40 parts by weight of the compound (III). Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention can be applied on a substrate, exposed through a mask having a predetermined pattern, developed, and then patterned, and further heated by heating. Thus, a polyimide film pattern can be obtained. The components of the photosensitive composition of the present invention are classified into a resin component (hereinafter, referred to as component I) and a photosensitizer component (hereinafter, referred to as component II, component III).
First, the component I commonly including the structural unit (1) will be described. [Component I] The resin component in the first photosensitive resin composition of the present invention is a polyamic acid derivative having the structural unit (1). This polyamic acid derivative is a precursor of polyimide and is typically synthesized by the following method. [First step] The tetracarboxylic dianhydride represented by the general formula (3) and an alcohol compound having at least one hydroxyl group directly bonded to an aromatic ring, or an amine compound having a molar ratio of about 1: 1 to 2 are used. The reaction is performed to produce a compound of the general formula (4).

[0033]

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[0034]

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(Where the tetracarboxylic dianhydride of the general formula (3) and A, R1,
R2 has the same meaning as A, R1, and R2 in the structural unit (1). [Second step] The compound (4) and the diamino compound (5)

[0036]

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(Where the aminomethyl group is bonded to the 2- and 5-positions or 2- and 6-positions of norbornane) and the dehydrating agent in a molar ratio of about 1: 1: 2 (or 2 or more). Reaction in an organic solvent. Thus, a polyamic acid derivative having the structural unit (1) is synthesized by a condensation reaction between the compound (4) and the diamino compound (5).

Examples of the tetracarboxylic dianhydride of the general formula (3) used in the first step reaction include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Dianhydride, 2,2 ', 3,3'
-Benzophenonetetracarboxylic dianhydride, 3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride , Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, 2,2'-
Bis (3,4-dicarboxyphenyl) -1,1,1,
3,3,3-hexafluoropropane dianhydride, 1,4
-Difluoropyromellitic acid, 1,4-bis (trifluoromethyl) pyromellitic acid, 1,4-bis (3,4-
Dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride, 2,2′-bis [4- (3,4-dicarboxyphenoxy) benzene] -1,1,1,3,
3,3-hexafluoropropane dianhydride, 2,3
6,7-naphthalenetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-naphthalenetetracarboxylic dianhydride, 3 , 4,9,10-Naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like. . These may be used alone or in combination of two or more.

The alcohol compound used in the first-stage reaction includes a compound of the formula R3-OH (provided that R3-O
And-is the same as R1 or R2). In the compound R3-OH, R3- is an organic device having at least one hydroxyl group bonded to an aromatic ring. Examples of such alcohol compounds include 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxyphenylethyl alcohol, 3-hydroxyphenylethyl alcohol, 4-hydroxyphenylethyl alcohol, -Hydroxyphenyl-3-propanol, 4-hydroxyphenyl-4-butanol, hydroxynaphthylethyl alcohol and the like. Among these, a compound represented by the general formula (6) is particularly preferable, and among them, 3-hydroxybenzyl alcohol is particularly preferable.

[0040]

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(Where p is a positive integer, preferably 1
4) The amine compound used in the first-stage reaction includes a compound represented by the formula R4-N (R5) H (where R4 is the above-mentioned R1, R
And R5 is hydrogen or a monovalent organic group). In this primary or secondary amine compound R4-N (R5) H, R
4 is an organic group having at least one hydroxyl group bonded to an aromatic ring. As such an amine compound, for example, 2-amine
Aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-4'-hydroxydiphenylethane, 4-amino-4'-hydroxydiphenylether, 2- (4'-aminophenyl) -2- (3 " -Hydroxyphenyl) propane, 2- (4'-aminophenyl) -2- (3 "-hydroxyphenyl) hexafluoropropane, 2- (3'-aminophenyl-2-
(3 ″ -hydroxyphenyl) propane, 2- (4′-
Aminophenyl) -2- (4 ''-hydroxyphenyl)
Propane, 2- (4′-aminophenyl) -2- (4 ″
-Hydroxyphenyl) hexafluoropropane. Among them, the compound represented by the general formula (7) is particularly preferred.

[0042]

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(Where R5 is hydrogen or a monovalent organic group, q is an integer of 0 or more, preferably 0 to 4) In the first step, the two compounds are prepared by using no solvent or At room temperature or under heating in a suitable solvent in the presence or absence of a suitable catalyst (temperature range 2).
5-200 ° C).

The diamino compound used in the reaction of the second step is represented by the formula (5)

[0045]

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(Where the aminomethyl group is bonded to the 2- and 5-positions or 2- and 6-positions of norbornane). As the condensing agent used in the reaction of the second step, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, cobalt acetate, manganese acetate, stannous chloride, stannic chloride, polyphosphoric acid, triphenyl phosphite, Bis-o-phenylene phosphate, N, N- (phenylphosphino) bis [2-
(3H) benzothiazolone], and the general formula RN = C = N-
A carbodiimide derivative represented by R ′, for example, dicyclohexylcarbodiimide (DCC) and the like can be mentioned.
As the organic solvent used for synthesizing the resin component containing the above structural unit (1), an aprotic polar solvent is usually used. Solvents such as hydrogen, tetrahydrofuran and dioxane can also be used. Specifically, ketone solvents such as cyclohexanone, acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate and butyl cellosolve acetate; ester solvents such as ethyl acetate, butyl acetate and isoamyl acetate; tetrahydrofuran , Dioxane and other ether solvents, N, N-dimethylformamide, N, N-dimethylacetamide (D
MAc), N-methyl-2-pyrrolidone (NMP), N
-Methyl-ε-caprolactam, γ-butyrolactone,
At least one solvent selected from the group consisting of solvents such as sulfolane, N, N, N ', N'-tetramethylurea, hexamethylphosphamide, toluene and xylene, or a mixed solvent thereof is used. The reaction of this second step is performed under cooling or heating (temperature range: -20 to 100).
C) for 30 minutes to 24 hours, preferably 1 to 8 hours. The polyamic acid derivative is synthesized in this manner, and it is particularly important to select a condensing agent and a reaction solvent. From the viewpoint that the reaction conditions are mild and do not contain ionic components as impurities, DCC is used as a condensing agent.
Is preferred. DMAc or NMP is used as a reaction solvent because the obtained polymer does not gel and has a sufficient dissolving power.
And the like. As described above, in the synthesis of the polyamic acid derivative having the structural unit (1), a monomer (carboxylic acid derivative) in which a substituent (the alcohol compound or the amine compound) is introduced into carboxylic acid in the first step of the reaction. Is formed, and then, in a second stage reaction, a polymer chain (polyamic acid derivative) having a substituent introduced into a side chain is formed by polycondensation of the monomer and a diamino compound. In addition, first, a polyamic acid of the general formula (2) is synthesized from a dicarboxylic anhydride and a diamino compound in a first step, and one or more hydroxyl groups bonded to an aromatic ring are added to the side chain in a second step. It can also be synthesized by a method of introducing an organic group having the compound.

[0047]

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(Here, B and D have the same meanings as described above.) In the present invention, the compound for introducing a substituent into the side chain of the polyamic acid derivative having the structural unit (1) (tetra- Examples of the compound which reacts with the carboxylic dianhydride (3) include, in addition to the above-mentioned alcohol compounds having one or more hydroxyl groups bonded to the aromatic ring and amine compounds, alcohols which do not contain a hydroxyl group bonded to the aromatic ring in the molecule. Compounds (phenol-containing compounds), amine compounds and the like can be used in combination.

When a compound not containing a hydroxyl group bonded to an aromatic ring or a phenol compound is used in combination, the amount used is 80 times the total amount of the compound used to introduce the substituent.
It is preferably at most mol%. 80 mol% used
If the ratio exceeds the above range, problems such as a decrease in the photosensitivity of the photosensitive composition, an extremely low dissolution rate in a developer, and deterioration of a formed polyimide film pattern occur.
More preferably, the compound is used in an amount of 60 mol% or less.

In this case, in the resin component of the photosensitive resin composition of the present invention, a polyamic acid derivative obtained by introducing the above compound and an organic group having a hydroxyl group bonded to an aromatic ring in the side chain are introduced. The polyamic acid derivative may form a mixture or may form a copolymer. The polyamic acid derivative containing the structural unit (1) synthesized by the above method is purified as follows. To the reaction solution of the polyamic acid derivative, methanol,
Ethanol, water, etc. are added to the condensing agent in a molar amount of 1 to 2 times, and the mixture is stirred for 1 to 4 hours to react the unreacted condensing agent, and the precipitate is filtered out and removed from the system. Wash with methanol, ethanol, or water 5 to 100 times the reaction solution. Thereafter, the polyamic acid is isolated and purified by drying in a vacuum at room temperature to 60 ° C.

The resin component in the second photosensitive resin composition of the present invention is a mixture of a polyamic acid derivative having the structural unit (1) and a polyamic acid derivative having the structural unit (2). Among these, the polyamic acid derivative having the structural unit (1) can be synthesized using the same compound according to the same method as the polyamic acid derivative in the first photosensitive resin composition described above.

The polyamic acid having the structural unit (2) is prepared by reacting the tetracarboxylic dianhydride (3) and the diamino compound (5) in a suitable solvent at room temperature or at -20 to 20.
It can be synthesized by reacting under cooling at a temperature of preferably -5 to 10C. The tetracarboxylic dianhydride (3), the diamino compound (5), and the solvent used in this reaction may be any compound that can be used for synthesizing the polyamic acid derivative having the structural unit (1).

The ratio of the polyamic acid derivative having the structural unit (1) and the polyamic acid having the structural unit (2) in the resin component of the second photosensitive resin composition is such that the total resin component is 100%. The amount by weight of the polyamic acid derivative is preferably 20 to 98 parts by weight, more preferably 40 to 95 parts by weight. If the polyamic acid derivative is less than 20 parts by weight, when forming a polyimide film pattern by photolithography technology or the like using the photosensitive resin composition, the dissolution rate of the exposed portion and the unexposed portion in the developing solution increases, The contrast of the target relief image is reduced. 2 parts by weight or more of the polyamic acid (the polyamic acid derivative is 98 parts by weight or less)
The reason for this is that the developability of the coating film is improved, and it is not necessary to use a strong developing solution. As the resin component in the second photosensitive resin composition, similarly to the first photosensitive resin composition, a polyamic acid derivative in which a substituent that does not include a hydroxyl group bonded to an aromatic ring in a side chain is introduced. You may make it contain.

The resin component in the third photosensitive resin composition of the present invention is a polyimide acid derivative having a copolymer structure containing the structural unit (1) and the structural unit (2). The polyamic acid derivative having the copolymer structure can be synthesized by a method similar to the method for synthesizing the polyamic acid derivative in the first photosensitive resin composition described above. [Component II] Next, component II of the heat-resistant photosensitive resin composition of the present invention will be described. Component I used in the present invention
I is a compound that is common to the first, second, and third compositions and generates an acid upon irradiation.
Examples of such compounds include the following compounds. i) trichloromethyl-s-triazines ii) diallyliodoniums iii) triallylsulfonium salts Among these compounds, trichloroazines include:
2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4- Methoxy-β-styryl) -bis (4,6-trichloromethyl) -S-triazine, 2-
(4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine and the like, as diaryliodonium salts, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethane Sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate and the like, and triarylsulfonium salts such as triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthio Phenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate It can be given over To such as preferable.

In addition, the following compounds can also be used. i) Oxazide derivative substituted by trihalomethyl group ii) Disulfone derivative iii) Imidosulfonate derivative iv) Nitrobenzyl derivative The amount of the compound that generates an acid upon irradiation with radiation is preferably 100 parts by weight of the polymer. 0.5 ~
20 parts by weight. If the addition amount is less than 0.5 parts by weight, the amount of acid generated by irradiation with radiation is small, and thus the sensitivity is reduced. On the other hand, if the amount exceeds 20 parts by weight, mechanical properties and the like after curing may be reduced.

Compounds that generate an acid upon irradiation can be used in combination with a sensitizer. Such sensitizers include, for example, coumarins, flavones, dibenzalacetones, dibenzacyclohexanes, chalcones, xanthenes, thiones having a substituent at the 3- and / or 7-position. Xanthenes, porphyrins, phthalocyanines, acridines, 9-
And anthracenes having a substituent at the 3-position. [Component III] Next, component III of the composition of the present invention will be described. Component III used in the present invention is selected from melamine resins and urea resins in which the N-position is substituted with a methylol group and / or an alkoxymethyl group. Examples of these include melamine resins, benzoguanamine resins, glycoluril resins, and alkoxymethylated urea resins. Of these, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, and alkoxymethylated urea resin are known methylolated melamine resins, methylolated benzoguanamine resins, and methylolated urea resins. It is obtained by converting to an alkoxy group.

With respect to the resin having an alkoxymethyl group, commercially available Cymel 300, 301, 303, 370, 325, 32 manufactured by Mitsui Cytec Co., Ltd.
7, 701, 266, 267, 238, 1141, 27
2,202,1156,1158,1123,117
0 and 1174 are effective, and Cymel 300 is particularly preferable. In addition, Nikarac MX-750, -032,
-706, -708, -40, -31, Nikarac MS
-11, Nikarac MW-30 (manufactured by Sanwa Chemical Co., Ltd.) and the like can also be used. These may be used alone or as a mixture.

As other crosslinking agents, hexamethoxymethylmelamine, dimethoxymethylurea and the like may be used alone. The amount of the compound capable of crosslinking by the action of these acids is preferably 3 to 40 parts by weight based on 100 parts by weight of the polymer. If it is less than 3 parts by weight, patterning is difficult due to insufficient crosslinking, while if it exceeds 40 parts by weight, the solubility in alkali becomes too high, so that the film thickness after development is reduced, and the polymer layer itself has There is a problem of deteriorating mechanical properties.

In constituting the resin composition of the present invention, NMP, DMAc, D
Amide solvents such as MF and DMI are common and most preferable, but other ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and THF, and γ-butyrolactone, cyclopentanone, It is possible to use solvents such as kilohexanone, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

In order to improve the coating properties of the above resin composition solution, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3 Solvents such as -butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl-3-methoxypropionate can be used by mixing in small amounts. In this case, a silane coupling agent may be used in combination for the purpose of increasing the adhesion to the substrate.

An example of the method of coating and imaging the photosensitive resin composition of the present invention is shown below. First, a resin composition varnish is applied on a substrate, and after removing the solvent, dried to 1 to 50 microns, preferably 5 to 30 microns. At this time, a silane coupling agent can be used in combination for the purpose of increasing the adhesion between the substrate and the resin composition film. Thereafter, a normal photomask is applied, and exposure and exposure are performed. In this state, 90-160 ° C., preferably 100
By performing the heat treatment at about 150 ° C., the sensitivity of the resin can be increased. The substrate that has been subjected to the photosensitive treatment is developed (etched) with an alkaline aqueous solution having an appropriate concentration.
At this stage, a fine pattern is transferred. The alkaline aqueous solution used at this time is an alkaline aqueous solution used in ordinary alkaline etching. For example, sodium hydroxide, an aqueous solution of an inorganic alkali such as potassium hydroxide,
Examples thereof include an aqueous solution of an organic alkali such as ethylamine, propylamine, butylamine, monoethanolamine, tetramethylammonium hydroxide (TMAH), and choline. Particularly, TMAH is generally used. These aqueous solutions may be used alone or in combination of two or more. Further, at the time of alkali etching, an organic solvent such as alcohol and ether, and various surfactants can be used in combination. After the development, the film is washed with a rinsing liquid such as water to obtain a negative image of the heat-resistant material precursor mixture.
The pattern thus obtained is subjected to a high temperature treatment (200 ° C.
(400 or less) can be converted into a heat-resistant resin having good patterning and excellent in heat resistance, chemical resistance, mechanical properties, and the like.

[0062]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by this.

Example 1 32.55 g of pyromellitic dianhydride (PMDA) was placed in a flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube.
149 mol) and 3-hydroxybenzyl alcohol 3
7.21 g (0.30 mol) was dissolved in 180 g of N, N-dimethylacetamide (DMAc).
After adding 3.79 g (0.30 mol), esterification was carried out with stirring at room temperature for 6 hours. Thereafter, dicyclohexylcarbodiimide (DCC) 61.9 at 5 ° C. or lower.
A solution obtained by dissolving 3 g in 90 g of DMAc was gradually added dropwise over about 90 minutes, and then 23.14 g of 2,5- (2,6-) diaminomethyl-bicyclo [2.2.1] heptane (NBDA) (0.
(15 mol) was dissolved in 90 g of DMAc, and the mixture was gradually added dropwise over about 2 hours to react. Thereafter, the reaction was carried out at room temperature for about 6 hours. Finally, 10 g of ethanol was added, and the mixture was further stirred for 1 hour. This reaction solution was dropped into pure water about 10 times the weight of the reaction solution to precipitate a white powder. The powder was collected by filtration and dried at 60 ° C. under reduced pressure for 24 hours to obtain 120.88 g of polyamic acid powder. The logarithmic viscosity of this polymer (dissolved in NMP so that the solid content concentration becomes 0.5 g / dl and measured at 35 ° C.) was 0.28 dl / g.
(This polymer is referred to as polymer I.) 100 parts by weight of this polymer I is dissolved in 250 parts by weight of NMP.
2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine: 2 parts by weight as a compound which generates an acid upon irradiation (this is referred to as photoacid generator II) As a resin compound capable of cross-linking by the action of an acid (this is referred to as a cross-linking agent III), 15 parts by weight of Cymel 300 manufactured by Mitsui Cytec Co., Ltd. are sufficiently mixed and dissolved, and filtered through a 0.2 μm Teflon (registered trademark) filter. As a result, a photosensitive resin composition varnish was obtained. Next, on a silicon wafer whose surface has been treated with a silane coupling agent,
This varnish was applied by dripping a very small amount and spin-coating. It was further dried at 80 ° C. under reduced pressure to obtain a coating film of about 5 μm. A photomask having a pattern drawn on the coating film was applied thereto, and irradiated with light of 365 nm (I-line) using a high-pressure mercury lamp. After exposure, the wafer was heat-treated at about 120 ° C., alkali-etched with a 10 wt% TMAH aqueous solution to dissolve and remove the exposed portion, and washed with a large amount of water to obtain a pattern image. The obtained pattern image was a clear line and space to a fine part.

Example 2 32.55 g (0.149 mol) of PMDA and N
MP 180 g was charged into the same apparatus as in Example 1, and NBDA 23.14 g (0.150 mol) was added thereto.
The reaction was carried out in the same manner as in Example 1. The logarithmic viscosity of the polyamic acid obtained here was 0.57 dl / g. 20 parts by weight of the polyamic acid varnish were mixed with 18 parts by weight of the polymer I and 35 parts by weight of NMP, and further, 0.36 parts by weight of the photoacid generator II used in Example 1 and a crosslinking agent III :
2.70 parts by weight were added and sufficiently mixed and dissolved. This resin composition solution was filtered with a filter as in Example 1,
This was a photosensitive resin composition solution. This solution was applied on a silicon wafer treated with a silane coupling agent and dried to form a coating film of about 5 μm. After masking this coating film in the same manner as in Example 1, an image was formed by irradiating i-rays, and after heat treatment, alkali etching was performed with a 3 wt% aqueous solution of TMAH to obtain a pattern image. The pattern image obtained here is also
The lines and spaces were clear to minute parts.

Example 3 PMDA (26.00 g, 0.119 mol), 3-hydroxybenzyl alcohol 37.50 g (0.30 mol)
l) is dissolved in 180 g of NMP and 23.75 g of pyridine
(0.30 mol), and the mixture was stirred at room temperature for 6 hours to perform esterification. Thereafter, the NBDA 23.
14 g (0.15 mol) and 90 g of NMP are added, and further 61.88 g (0.30 mol) of DCC and 60 g of NMP are added.
Was added dropwise. After stirring this solution at room temperature for about 6 hours, 6.55 g (0.03 mol) of PMDA was further added, and stirring was continued for 6 hours. A white powder of a polyamic acid ester was obtained from this solution in the same manner as in Example 1. The logarithmic viscosity of this polyamic acid ester is 0.33 dl / g.
Met. This polymer powder: 100 parts by weight and NMP: 1
80 parts by weight, photoacid generator II: 3 parts by weight, crosslinking agent I
II: 15 parts by weight were mixed and dissolved to obtain a photosensitive resin composition solution. This solution was similarly filtered, spin-coated on a silicon wafer surface-treated with a silane coupling agent, and dried to form a coating film of about 5 μm. This substrate was masked in the same manner as in Example 1 and patterned by irradiating with i-line. This was subjected to alkali etching with a 3 wt% TMAH aqueous solution to dissolve and remove the exposed portion. The image obtained here was a clear line and space up to a fine part.

[0066]

According to the present invention, there is provided a photosensitive resin composition which can be developed (etched) with an aqueous alkali solution and can obtain a clear image up to a fine portion. The obtained polyimide layer had excellent heat resistance, mechanical strength, and electrical insulation inherent to polyimide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 79/08 C08L 79/08 A 5F058 G03F 7/004 501 G03F 7/004 501 7/029 7/029 H01L 21/312 H01L 21/312 D H05K 3/28 H05K 3/28 D 3/46 3/46 TF term (reference) 2H025 AB16 AB17 AC01 AD03 BE00 BE04 BE07 BE08 CB25 CB45 CC17 CC20 FA17 FA29 4J002 CC16X CC18X CC19X CC23X CC24X CM04W EB116 EH036 ES006 EU186 EU216 EV046 EV216 EV256 EV296 FD156 GP03 GQ01 4J043 PA19 QB15 QB24 QB26 QB32 QB33 RA35 SA06 TA02 TA12 TA13 TA22 TA31 TA32 TA47 TA53 TA71 VA081 UA122 UA132 UA142 UA152 UB UB UB UB UB YB31 YB35 YB44 ZB22 ZB50 5E314 AA27 AA36 GG03 GG08 5E346 AA12 AA17 CC10 HH08 HH11 HH18 5F058 AC02 AC06 AC07 AF04 AG01 AH01

Claims (6)

[Claims] 1. A compound of the general formula (1) (Wherein A is a tetravalent organic group, B is a group shown below, R1 and R2 represent a monovalent organic group or a hydroxyl group, and R1 and R2
Represents an organic group having at least one hydroxyl group bonded to an aromatic ring), a polyamic acid derivative (I) having a structural unit represented by the formula (I), a compound (II) that generates an acid upon irradiation, and an acid A photosensitive resin composition comprising a compound (III) capable of crosslinking a polyimide acid derivative having a structural unit represented by the above general formula (1) by the action of (III). 2. A compound of the general formula (1) (Wherein, A is a tetravalent organic group, B is a group shown below, R1 and R2 represent a monovalent organic group or a hydroxyl group, and R1 and R2
At least one of which represents an organic group having at least one hydroxyl group bonded to an aromatic ring) and a polyamic acid derivative having a structural unit represented by the general formula (2): (Wherein B represents a group equivalent to the formula (1), D represents a tetravalent organic group, and D may be the same as or different from A) with a polyamic acid having a structural unit represented by It contains a mixture (I), a compound (II) which generates an acid upon irradiation with radiation, and a compound (III) which can crosslink a polyimide acid derivative having a structural unit represented by the above general formula (1) by the action of an acid. A photosensitive resin composition characterized in that: 3. A compound of the general formula (1) (Where A is a tetravalent organic group, B is a group shown below, R1 and R2 represent a monovalent organic group or a hydroxyl group, and R1 and R2
At least one of them represents an organic group having at least one hydroxyl group bonded to an aromatic ring) and the general formula (2): (Wherein B represents a group equivalent to the formula (1), D represents a tetravalent organic group, and D may be the same as or different from A). Polyamic acid derivative (I) having a compound represented by the formula (I)
I) a compound capable of crosslinking a polyamic acid derivative having a structural unit represented by the general formula (1) by the action of an acid (II)
(I) A photosensitive resin composition comprising: 4. The photosensitive resin according to claim 1, comprising 100 parts by weight of the polyamic acid derivative (I), 0.5 to 20 parts by weight of the compound (II), and 3 to 40 parts by weight of the compound (III). Composition. 5. The method according to claim 2, wherein the mixture (I) is
A photosensitive resin composition containing 0 parts by weight, 0.5 to 20 parts by weight of a compound (II), and 3 to 40 parts by weight of a compound (III). 6. A photosensitive resin according to claim 3, comprising 100 parts by weight of the polyamic acid derivative (I), 0.5 to 20 parts by weight of the compound (II), and 3 to 40 parts by weight of the compound (III). Composition.