JPH10307393A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition capable of developing with alkali and superior in sensitivity and resolution. SOLUTION: This photosensitive composition contains (A) a polyamide acid derivative having a structural unit represented by the formula in which R<1> is a tetravalent organic group, R<2> is a divalent organic group and each of R<3> and R<4> is a univalent organic group or a hydroxyl group and at least one of them is an organic group having >=1 hydroxyl group combining with an aromatic ring, (B) a compound producing an acid by irradiating with radiation and (C) a compound capable of cross-linking the polyamide acid derivative (A) by 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 for an insulating material of an electronic component or a passivation film, a buffer coat film, an interlayer insulating film or the like in a semiconductor device. .

[0002]

2. Description of the Related Art Polyimide resins have excellent heat resistance, electrical properties, mechanical properties, and the like, and are therefore used for surface protection films and interlayer insulating films of semiconductor devices. In recent years, demands for polyimide resins excellent in mechanical properties, heat resistance, and the like have been increased with the increase in integration and size of semiconductor elements.

As such a polyimide resin, a photosensitive polyimide resin has been widely used because of its feature that a pattern forming process can be simplified and a complicated manufacturing process can be shortened. Therefore, issues remain in terms of safety and environmental issues. Therefore, recently, a photosensitive resin that can be developed with an alkaline aqueous solution has been proposed. For example, the following techniques are known. (1) Polyamide acid is mixed with a compound having an amino group, an amide group, a urethane group, etc., and after exposure in the presence of a photoinitiator,
(2) A method of mixing quinonediazide with a salt of a polyamic acid and an amine compound having a phenolic hydroxyl group (see JP-A-6-161102) (3) Polyamic acid (See Japanese Patent Application Laid-Open No. 5-5995) The above-mentioned ones are based on polyamic acid, but these show relatively good developability. But,
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. Also, it is difficult to say that the light sensitivity is sufficiently high.

A mixture of a polybenzoxazole precursor and a diazoquinone compound (Japanese Patent Publication No. 1-4686)
No. 2) or a polyamic acid in which a phenol moiety is introduced via an ester bond (Japanese Patent Application Laid-Open No. Hei 4-21805).
Although compounds having a phenolic hydroxyl group instead of a carboxylic acid, such as 1), are known, these compounds have insufficient developability and photosensitivity, and have problems such as peeling of a resin from a substrate. There is.

In order to improve such developability and adhesion,
Mixtures of a polyamic acid having a siloxane moiety in the polymer skeleton (see JP-A-4-31861 and JP-A-4-46345) have also been proposed, but these have improved developability, As described above, the light sensitivity is insufficient. On the other hand, a chemically amplified photosensitive composition comprising a resin component in which a specific protecting group is introduced into a carboxyl group of a polyimide precursor and a compound exhibiting acidity by irradiation with actinic rays (Japanese Patent Laid-Open No. 4-120171). Gazette). However, in this case, when a protecting group such as a tetrahydropyranyl group, a 1-ethoxyethyl group, a methoxymethyl group, or a trimethylsilyl group is used as the protecting group, the sensitivity is good, but these protecting groups are easily removed. In addition, problems of storage stability in a solution state, and heat treatment after exposure (hereinafter referred to as PEB).
Is practically inadequate, for example, the pattern shape (resolution) and the sensitivity are greatly affected by the standing time until reaching or the PEB temperature.

Further, methyl and ethyl groups as protecting groups,
When using a propyl group, a butyl group, a benzyl group, etc.,
Although the storage stability in the solution is improved, even after the acid generation by irradiation with actinic rays, the protective group is not sufficiently eliminated even through the PEB step, which cannot be said to be a practical level material.

[0007]

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

[0008]

The first photosensitive composition of the present invention comprises (A) 100 parts by weight of a polyamic acid derivative having a structural unit represented by the following general formula (1):

[0009]

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(Wherein, R ^{1 represents a} tetravalent organic group, R ^{2 represents} a divalent organic group, R ³ , R ^{4 represents a} monovalent organic group or a hydroxyl group, at least one of which is bonded to an aromatic ring. An organic group having at least one hydroxyl group.), (B) 0.5 to 20 parts by weight of a compound capable of generating an acid upon irradiation, and (C) a structure represented by the above general formula (1) by the action of an acid. A photosensitive composition comprising 3 to 40 parts by weight of a compound capable of crosslinking a polyamic acid derivative having a unit.

The second photosensitive composition of the present invention has (A) a polyamic acid derivative having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). 100 parts by weight of a mixture of polyamic acids,

[0012]

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(Wherein, R ^{1 represents a} tetravalent organic group, R ^{2 represents} a divalent organic group, R ³ and R ^{4 represent a} monovalent organic group or a hydroxyl group, at least one of which is bonded to an aromatic ring. An organic group having at least one hydroxyl group.),

[0014]

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(Wherein R ⁵ represents a tetravalent organic group, and R ⁶ represents a divalent organic group.) (B) Compounds which generate an acid by irradiation with radiation 0.5 to 2
A photosensitive composition comprising: 0 parts by weight; and 3 to 40 parts by weight of 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 (C). Things.

The third photosensitive composition of the present invention comprises (A) a polyamic acid derivative 1 having a copolymer structure containing structural units represented by the following general formulas (1) and (2):
00 parts by weight,

[0017]

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(Wherein, R ^{1 represents a} tetravalent organic group, R ^{2 represents} a divalent organic group, R ³ , R ^{4 represents a} monovalent organic group or a hydroxyl group, at least one of which is bonded to an aromatic ring. An organic group having at least one hydroxyl group.),

[0019]

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(In the formula, R ⁵ represents a tetravalent organic group, and R ⁶ represents a divalent organic group.) (B) Compounds which generate an acid upon irradiation with radiation 0.5 to 2
A photosensitive composition comprising: 0 parts by weight; and 3 to 40 parts by weight of 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 (C). Things. These photosensitive compositions of the present invention are coated on a substrate, exposed through a mask having a predetermined pattern, can be patterned by developing, and further, by heating this, polyimide film pattern Can be obtained. Hereinafter, the photosensitive composition of the present invention will be described in detail.

The photosensitive composition of the present invention comprises a resin component (hereinafter referred to as A component) and a photosensitizer component (hereinafter referred to as B component,
C component). First, the component A that commonly includes the structural unit (1) will be described. <Component A> The resin component in the first photosensitive 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] First, a tetracarboxylic dianhydride represented by the following general formula (3) and an alcohol compound having at least one hydroxyl group directly bonded to an aromatic ring, or an amine compound thereof, have a molar ratio of about 1: 1 and 2, and the following general formula (4)
To produce the compound

[0022]

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[0023]

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(Where the tetracarboxylic dianhydride of the general formula (3) and R ¹ , R ³ ,
R ⁴ has the same meaning as R ¹ , R ³ and R ⁴ in the structural unit (1). [Second step] The compound (4) and the diamino compound NH ₂
-R ² -NH ₂ (R ² is R ² as defined in the structural unit (1)) and, a dehydrating agent, the molar ratio of about 1: 1: 2 (or more), is reacted in an organic solvent. Thus, the polyamic acid derivative having the structural unit (1) is synthesized by the condensation reaction between the compound (4) and the diamino compound.

Examples of the tetracarboxylic dianhydride of the general formula (3) used in the first-stage reaction include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Acid dianhydride, 1,4,5,8
-Naphthalenetetracarboxylic dianhydride, 2,3,6
7-naphthalenetetracarboxylic dianhydride, 1,2,2
5,6-naphthalenetetracarboxylic dianhydride, 3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic acid Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [5-
(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [5- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenyl] Sulfonic dianhydride, bis (3,4-dicarboxyphenyl] ether dianhydride, bis (3,4-dicarboxyphenyl] methane dianhydride, berylen-3,4,9,10 tetracarboxylic dianhydride Product, butanetetracarboxylic dianhydride, 2,
At least one compound selected from the group consisting of 2 '-(3,4-dicarboxyphenylhexafluoropropane dianhydride can be used.

The alcohol compound used in the first-stage reaction includes a compound represented by the formula R ⁷ —OH (provided that R ⁷ —O—
Compounds can be used represented by the same said R ³ or R ^4). In the compound R ⁷ —OH, R ⁷ — is an organic group 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 them, a compound represented by the following general formula (5) is particularly preferred, and among them, 3-hydroxybenzyl alcohol is most preferred.

[0028]

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(Where p is a positive integer, preferably 1 to
4) The amine compound used in the first-stage reaction includes a compound represented by the formula R ⁸ —N (R ⁹ ) H (where R ⁸ is R ³ or R ⁴ , and R ⁹ is hydrogen or a monovalent organic group). The primary or secondary amine compound represented by the formula (1) can be used. In the primary or secondary amine compound R ⁸ —N (R ⁹ ) H, R ⁸ — is an organic group having at least one hydroxyl group bonded to an aromatic ring.
Examples of such an amine compound include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-4′-hydroxydiphenylethane, 4-amino-4′-hydroxydiphenylether, and 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.

Of these, compounds represented by the following general formula (6) are particularly preferred.

[0031]

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(Where R ⁹ is hydrogen or a monovalent organic group,
q is an integer of 0 or more, preferably 0 to 4) In this first step, the two kinds of compounds are used without a solvent or in a suitable solvent in the presence of a suitable catalyst or in the presence of a catalyst. Without, at room temperature or under heating (temperature range:
(About 25-200 ° C.).

On the other hand, the diamino compound (NH ₂ —R ² —NH ₂ ) used in the second-stage reaction includes, for example, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3 ′
-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone, 4,4'-diaminodiphenylketone, 3,4'-diaminodiphenylketone, 2,2 '-Bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amino Phenoxy)
Benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-
Aminophenyl) -2-pentene, 1,4-bis (α,
α-dimethyl-4-aminobenzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-
2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,
3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diaminodiphenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2, 2-bis
[4- (4-aminophenoxy) phenyl] propane,
2,2-bis [4- (4-aminophenoxy) phenyl]
Hexafluoropropane, 2,2bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,
4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4-
(Α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, bis (4-aminophenyl)
Aromatic diamines such as dimethylsilane and bis (4-aminophenyl) tetramethylsiloxane, and hydrogen atoms of aromatic nuclei of these aromatic diamines are chlorine, fluorine, bromine, methyl, methoxy, cyano, A compound substituted by at least one substituent selected from the group consisting of phenyl groups, and 3,5-diamino-1
-Hydroxybenzene, 3,3'-dihydroxy-4,
4'-diaminobiphenyl, 4,4'-dihydroxy-3,3'-diaminobiphenyl, 2,2-bis (4-amino-3-hydroxyphenyl) propane, bis (3-
Amino-4-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane,
2,2′-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2- (3hydroxy-4
-Aminophenyl) -2- (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (Γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, 4,4′-diaminobiphenyl, 4,4′-diaminobenzophenone, Phenylindanediamine, 3,3 '
-Dimethoxy-4,4'-diaminobiphenyl, 3,3 '
-Dimethyl-4,4'-diaminobiphenyl, o-toluidinesulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl)
Anthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, 4,4′-diaminobenzamylide, and represented by the following general formula (7) At least one diamino compound selected from the group consisting of compounds can be used.

[0034]

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(Where 1 is an integer of 2 to 12) As the dehydrating 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], a general formula RN = C =
A carbodiimide derivative represented by NR ′, for example, dicyclohexylcarbodiimide (DCC) and the like. As the organic solvent used for synthesizing the resin component containing the structural unit (1), an aprotic polar solvent is usually used. However, regarding the synthesis of the polyamic acid derivative used in the present invention, an aromatic solvent is used. Solvents such as hydrocarbons, 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 celloselb, methyl celloserub acetate, and butyl celloserub acetate; and ester solvents such as ethyl acetate, butyl acetate, and isoamyl acetate. solvent,
Ether solvents such as tetrahydrofuran and dioxane,
N, N-dimethylformamide, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-methyl-ε-caprolactam, γ-butyrolactone, sulfolane, N, N, N ′, N′— At least one solvent selected from the group consisting of solvents such as tetramethyl urea, hexamethyl phosphoamide, toluene, and xylene, or a mixed solvent thereof is used. The reaction of this second step is performed under cooling or heating (temperature range: -2
0-100 ° C) for about 30 minutes to 24 hours, preferably about 1 to 8 hours. The polyamic acid derivative is synthesized in this manner. Here, it is particularly important to select the condensing agent and the reaction solvent used in the second step.
As a condensing agent, DCC is preferred from the viewpoint that the reaction conditions are mild and do not contain an ionic component as an impurity.
As the reaction solvent, an amide solvent such as DMAc or NMP is preferable because the obtained polymer does not gel and has a sufficient dissolving power. As described above, the structural unit (1)
In the synthesis of a polyamic acid derivative having the formula (I), a monomer (carboxylic acid derivative) in which a substituent (the alcohol compound or the amine compound) is introduced into a carboxylic acid is formed in a first-stage reaction, and then a second-stage reaction is performed. In the reaction, by polycondensation of the monomer and a diamino compound,
A polymer chain (polyamic acid derivative) having a substituent introduced into a side chain is formed. In addition, first, a polyamic acid represented by the following general formula (8) is synthesized from a dicarboxylic anhydride and a diamino compound in a first step, and in a second step, one or more hydroxyl groups bonded to an aromatic ring are added to a side chain thereof. It can also be synthesized by a method of introducing an organic group having

[0036]

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In the present invention, the compound for introducing a substituent into the side chain of the polyamic acid derivative having the structural unit (1) (the compound which reacts with the tetracarboxylic dianhydride (3) in the first step) )), In addition to the above-mentioned alcohol compounds and amine compounds having one or more hydroxyl groups bonded to aromatic rings, alcohol compounds not containing hydroxyl groups bonded to aromatic rings in the molecule (phenol-containing compounds), amine compounds, etc. You can also.

Examples of such alcohol compounds include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, 1-hexanol, and benzyl alcohol. , Methylbenzyl alcohol, cinnamyl alcohol, methoxybenzyl alcohol, allyl alcohol, 2-hydroxyethyl methacrylate, and the like. Examples of the phenol compound include phenol, cresol, xylenol, butylphenol, allylphenol, and methoxyphenol.

Examples of the amine compound include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, aniline, toluidine, ethylaniline, and benzylamine. When a compound or a phenol compound containing no hydroxyl group bonded to the aromatic ring as described above is used in combination,
The amount used is preferably about 80 mol% or less of the total amount of the compound used for introducing the substituent. When the amount exceeds 80 mol%, problems such as a decrease in photosensitivity of the photosensitive composition, an extremely low dissolution rate in a developer, and deterioration of a formed polyimide film pattern occur. That's why. Further, the more preferred amount of the compound to be used is 60 mol% or less.

In this case, in the resin component of the photosensitive 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. Polyamic acid derivative,
A mixture may be formed, or a copolymer may be formed. The polyamic acid derivative containing the structural unit (1) synthesized by the above method is purified as follows. That is, to the reaction solution of the polyamic acid derivative, methanol, ethanol, water and the like are added in an amount of about 1 to 2 times the molar amount of the dehydrating agent, and the mixture is stirred for 1 to 4 hours to react the unreacted dehydrating agent to precipitate The solution was removed by filtration and the resulting solution was
Wash with methanol, ethanol or water 5 to 100 times the reaction solution. Thereafter, the polyamide acid derivative is isolated and purified by drying at room temperature to 60 ° C. in a vacuum.

The resin component in the second photosensitive composition of the present invention is a mixture of a polyamic acid derivative having the structural unit (1) and a polyamic acid having the structural unit (2). Among them, 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 above-mentioned first photosensitive composition.

The polyamic acid having the structural unit (2) is obtained by reacting a tetracarboxylic dianhydride (3) with a diamino compound (NH ₂ —R ² —NH ₂ ) at room temperature or in a suitable solvent. It can be synthesized by reacting under cooling at 20 to 20 ° C, preferably -5 to 10 ° C. The tetracarboxylic dianhydride (3), the diamino compound (NH ₂ —R ² —NH ₂ ), and the solvent used in this reaction can be used to synthesize a polyamic acid derivative having the structural unit (1). Any compound may be used.

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 composition is such that the total resin component is As 100 parts by weight, 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 composition, the dissolution rate of the exposed part and the unexposed part in the developing solution is increased, The contrast of the target relief image is reduced. The reason why the polyamic acid is used in an amount of 2 parts by weight or more (the polyamic acid derivative is 98 parts by weight or less) is because the developability of the coating film is improved and a strong developing solution may not be used.

As the resin component in the second photosensitive composition, as in the first photosensitive composition, polyamide having a substituent having no hydroxyl group bonded to an aromatic ring in the side chain is introduced. An acid derivative may be contained. The resin component in the third photosensitive composition of the present invention is a polyamic 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 composition described above. (Synthesis method of copolymer structure polyamic acid derivative)
As a first step, tetracarboxylic dianhydride (3);
The compound (4) is synthesized by reacting an alcohol compound having one or more hydroxyl groups bonded to an aromatic ring with the amine compound in a molar ratio of 1 to 1 to 2. In this reaction, the two compounds are used without a solvent or in an appropriate solvent.
It is performed at room temperature or under heating.

Next, as a second step, the compound (4)
And a diamino compound (NH ₂ —R ² —NH ₂ ) and a dehydrating agent are reacted in the solvent at a molar ratio of s: (s + t): 2s (s and t are positive integers). This reaction is carried out under cooling or heating for about 1 to 8 hours, preferably 4 hours or more. Further, as a third step, t-mol of tetracarboxylic dianhydride (3) is added to the above solution,
For about 1 to 8 hours, preferably 4 hours or more.

Thus, a polyamic acid derivative having a copolymer structure containing the structural unit (1) and the structural unit (2) can be synthesized. A tetracarboxylic dianhydride (3), an alcohol compound having at least one hydroxyl group bonded to an aromatic ring, an amine compound used in the synthesis of the resin component in the third photosensitive composition of the present invention, The diamino compound (NH ₂ —R ² —NH ₂ ), the dehydrating agent, and each solvent may be any compounds used in the synthesis of the resin component in the first and second photosensitive compositions.

In the synthesis of the resin component in the third photosensitive composition, an alcohol compound having at least one hydroxyl group bonded to an aromatic ring as described above in the same manner as in the first photosensitive composition; An alcohol compound and an amine compound that do not contain a hydroxyl group bonded to an aromatic ring can be used together with the compound. The structural unit (1) and the structural unit (2) in the copolymer structure of the resin component.
The ratio (s / t) is not particularly limited because the final resin characteristics vary depending on the resin material used, but is preferably 1 to 20. If less than 1,
The solubility in the alkali developing solution is increased, and a sufficient difference in solubility between the exposed portion and the unexposed portion in the developing solution cannot be obtained during development. Conversely, when the value of t is small and s / t is larger than 20, the solubility of the coating film is insufficient and the developability is insufficient.

The polyamic acid derivative having the structural unit of the general formula (1) used in the first and second photosensitive compositions thus obtained, and the above-mentioned general compound used in the third photosensitive composition The molecular weight of the copolymer having the structural units of formulas (1) and (2) is 0.15 to less in terms of reduced viscosity (concentration = polymer: 1 g / NMP: 100 mL, 30 ° C.).
0.6 [dL / g], preferably 0.25 to 0.5 [dL / g]
g]. In the polymer of the formula (2) used in the second composition, the ratio is 0.3 to 0.8. <Component B> Next, (B) of the heat-resistant photosensitive composition of the present invention.
The components will be described. The component (B) used in the present invention 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: tris (2,4,6-trichloromethyl) -s-triazine,
2-phenyl-bis (4,6-trichloromethyl) -s
-Triazine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) ) -Bis (4,6-
Trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl)- s-triazine, 2
-(3-methylthiophenyl) bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) )-Screw (4, 6
-Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl)
-S-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine,
-(3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-
(4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, -(2-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine and the like. ii) Diallyliodoniums: diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxy Phenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-
Methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, Bis (4-ter-butylphenyl)
Iodonium trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate and the like. iii) Triallylsulfonium salts: triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluene Sulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4
-Methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate,
4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexa Fluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate and the like.

Among these compounds, trichloromethyl-S-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine and 2- (4-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 trifluoro Acetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate,
Methoxyphenylphenyl iodonium trifluoroacetate and the like, and triarylsulfonium salts such as triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate,
Preferred examples include methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, and 4-phenylthiophenyldiphenyltrifluoroacetate.

In addition, the following compounds can also be used. (1) An oxadiazole derivative substituted with a trihalomethyl group.

[0051]

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(2) Disulfone derivatives.

[0053]

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(3) Imidosulfonate derivatives.

[0055]

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(4) Nitrobenzyl derivatives.

[0057]

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(Here, R12 represents an alkyl group, and represents an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.) Is preferably 0.5 to 100 parts by weight of the polymer.
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, 3-position and / or
Or a coumarin having a substituent at the 7-position, a flavone,
Dibenzalacetones, dibenzal cyclohexanes,
Examples include chalcone, xanthene, thioxanthene, porphyrin, phthalocyanine, acridine, and anthracene having a substituent at the 9-position. <Component C> Next, the component (C) of the composition of the present invention will be described. The component (C) 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, urea resins, alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins. Among 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 resin. It is obtained by converting to an alkoxymethyl group.

Examples of the type of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group and a butoxymethyl group, and commercially available Cymel 300, 3
01, 303, 370, 325, 327, 701, 26
6,267,238,1141,272,202,11
56, 1158, 1123, 1170, 1174, F
R65,300 [manufactured by Mitsui Cyanamid Co., Ltd.], Nikarac MX-750, -032, -706, -708,-
40, -31, Nikarac MS-11, Nikarac MW
-30 (manufactured by Sanwa Chemical Co., Ltd.) or the like can be preferably used. These compounds can be used alone or as a mixture.

In addition, as the crosslinking agent, a monomer of the resin described above may be used, and examples thereof include hexamethoxymethylmelamine and dimethoxymethylurea. 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 the addition amount is less than 3 parts by weight, crosslinking may be insufficient and patterning may be difficult. Also, 40
If the amount is more than 100 parts by weight, the alkali solubility of the entire composition becomes too high, so that the residual film ratio after development tends to decrease or the mechanical properties after curing tend to decrease. The composition of the present invention is used in the form of a varnish by dissolving the polymer of the component (A) in a solvent. As solvents, NMP, DMAc,
γ-butyrolactone, cyclopentanone, cyclohexanone, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and the like may be used alone or in combination. For the purpose of improving the coating properties, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, , 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, and other solvents can be used in combination. At this time, an additive such as a silane coupling agent may be added to enhance the adhesiveness to the base material. Next, an example of a method for forming an image using the heat-resistant photosensitive composition thus obtained will be described. First, the film thickness of this composition varnish after drying on a substrate is 1 to 50 μm, preferably 5 to 30 μm.
m. At this time, it is also possible to previously treat the substrate with an adhesion aid such as a silane coupling agent. After drying the applied coating film, it is exposed through a normal photomask and then subjected to a heat treatment (PE
Perform B). This PEB step is a process for sensitizing the sensitivity of the present composition, and is indispensable for achieving the object of the present invention. The processing temperature is preferably from 90 to 160 ° C, and more preferably from 100 to 150 ° C, in consideration of the sensitivity, the obtained pattern shape, and the like. The substrate that has been subjected to the heat treatment after irradiation with radiation can be transferred with a fine resin pattern onto the substrate by being developed with an alkali aqueous solution having an appropriate concentration. The developer used at this time is preferably one capable of completely dissolving and removing the exposed film within an appropriate time, and is preferably an inorganic alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, or propylamine, butylamine, monoethanolamine, tetraethanol or the like. An organic alkaline aqueous solution of methylammonium hydroxide (TMAH), choline or the like is used alone or in combination of two or more. In addition, the alkaline aqueous solution may contain an organic solvent such as an alcohol and various surfactants as necessary. After development, a negative image of the heat-resistant material precursor is obtained by washing with a rinse solution. The image thus obtained was subjected to a high-temperature heat treatment (about 200
To 400 ° C.), it can be converted to a heat-resistant material having excellent heat resistance, chemical resistance, and mechanical properties, and becomes a cured product having a good relief pattern.

[0062]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described based on examples.

[0063]

EXAMPLE 1 68.9 parts by weight (0.21 mol) of benzophenonetetracarboxylic dianhydride (BTDA) and 52.1 parts by weight (0.42 mol) of 3-hydroxybenzyl alcohol (3HBA) were N, N 'Dimethylacetamide (DM
Ac) was dissolved in 750 parts by weight, and 33.3 parts by weight (0.42 mol) of pyridine was added, followed by stirring at room temperature for 16 hours to carry out esterification. Then, a solution prepared by dissolving 86.7 parts by weight (0.42 mol) of dicyclohexylcarbodiimide (DCC) in 80 g of DMAc was added dropwise under ice cooling, and then 4,4'-diaminodiphenyl ether (ODA) was added.
A solution obtained by dissolving 0 parts by weight (0.19 mol) in 100 g of DMAc was added to carry out a reaction. Thereafter, the mixture was returned to room temperature and reacted for 3 hours. Finally, ethanol was added, and the mixture was further stirred for 1 hour. After removing the insoluble matter by filtration, the reaction solution was added dropwise to 10 liters of distilled water, and the precipitate was collected by filtration and collected under reduced pressure. By drying, a polyamic acid ester (polymer 1) was obtained. The reduced viscosity of this polymer (concentration = polymer: 1 g / NMP: 100 mL, 30 ° C.) is 0.35.
[dL / g]. Next, the polymer was dissolved in 250 parts by weight of NMP based on 100 parts by weight of the polymer, and the component (B) was dissolved.
2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine: 2 parts by weight and component (C) [Cymer 300 manufactured by Mitsui Cyanamid Co., Ltd.]: 15 After mixing by weight, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive varnish. The varnish was spin-coated on a silicon wafer previously treated with a silane coupling agent to obtain a coating film having a thickness of 5 μm after drying. This coating film was irradiated with ultraviolet light at a different exposure amount using an ultra-high pressure mercury lamp through a mask on which a pattern was drawn. After the exposure, the silicon wafer was heated on a hot plate at 120 ° C. for 5 minutes. Thereafter, the exposed portion was dissolved and removed by immersion in a 10% TMAH aqueous solution for 10 minutes, and then rinsed with water. 1μm in result, irradiation of the exposure dose 100 mJ / cm ²
Were resolved, and a good pattern could be obtained.

[0064]

Example 2 BTDA: 38.7 parts by weight (0.12 mol)
Was added to NMP: 200 parts by weight, and ODA: 20.
0 parts by weight (0.1 mol), bis (γ-aminopropyl)
After adding 2.5 parts by weight (0.01) of tetramethyldisiloxane under ice-cooling, the mixture was reacted at room temperature for 10 hours. The reduced viscosity of the polyamic acid (polymer 2) thus obtained was 0.55. Next, a solution of this polymer 2: 20
A solution prepared by dissolving 18 parts by weight of polymer in 35 parts by weight of NMP was mixed with 35 parts by weight of NMP, and 0.36 parts by weight and 2.36 parts by weight of the same components (B) and (C) used in Example 1 were added.
7 parts by weight were added and mixed well. Next, this is 0.2 μm
To obtain a photosensitive varnish.

The varnish was spin-coated on a silicon wafer to obtain a coating having a thickness of 8 μm after drying. This coating film was irradiated with ultraviolet light at a different exposure amount using an ultra-high pressure mercury lamp through a mask on which a pattern was drawn. After the exposure, the silicon wafer was heated on a hot plate at 150 ° C. for 5 minutes. Thereafter, the exposed portion was dissolved and removed by immersion in a 3% aqueous solution of TMAH for 8 minutes, followed by rinsing with water. As a result, 2 μm lines and spaces were resolved by irradiation with an exposure amount of 150 mJ / cm ² , and a good pattern could be obtained.

[0066]

Example 3 BTDA: 40 parts by weight (0.12 mol),
3HBA: 30 parts by weight (0.24 mol) in DMAc: 1
And pyridine: 19 parts by weight (0.24 parts by weight).
Mol), and the mixture was stirred at room temperature for 16 hours to perform esterification. Thereafter, ODA: 30 parts by weight (0.1%) under ice cooling.
15 mol) dissolved in 60 parts by weight of DMAc was added, and then 49.5 parts by weight (0.24 mol) of DCC was added to Dc.
MAc: A solution dissolved in 50 parts by weight was added dropwise. Then, after returning to room temperature and reacting for 3 hours, BTDA: 9.7
Part by weight (0.03 mol) was gradually added, and the mixture was further reacted for 3 hours. After removing the insoluble matter by filtration, the reaction solution was added dropwise to 10 liters of distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester having a copolymer structure (polymer 3). Reduced viscosity of this polymer (concentration = polymer: 1 g / NMP: 100
mL, 30 ° C.) was 0.25 [dL / g]. Next, 100 parts by weight of this polymer 3 was dissolved in 180 parts by weight of NMP, and 3 parts by weight and 15 parts by weight of the same components (B) and (C) used in Example 1 were added, respectively. Mix well. Next, this was filtered through a 0.2 μm Teflon filter to obtain a photosensitive varnish. The varnish was spin-coated on a silicon wafer previously treated with a silane coupling agent to obtain a coating having a thickness of 5 μm after drying. This coating film was irradiated with ultraviolet light at a different exposure amount using an ultra-high pressure mercury lamp through a mask on which a pattern was drawn. After the exposure, the silicon wafer was heated on a hot plate at 120 ° C. for 5 minutes. After this, 3% of TM
The exposed portion was dissolved and removed by immersion in an AH aqueous solution for 3 minutes, and then rinsed with water. As a result, the exposure amount was 100 m
A line and space of 1 μm was resolved by irradiation of J / cm ² , and a good pattern could be obtained.

[0067]

Comparative Example 1 A photosensitive varnish was prepared in the same manner as in Example 1 except that 100 parts by weight of the polymer 2 was used, and the patterning performance was examined. As a result, although the alkali developability was improved, there was no difference in solubility between the exposed and unexposed areas, and all the patterns flowed under any PEB conditions and development conditions. This indicates that a polymer having a phenolic hydroxyl group is essential for this photosensitive composition.

[0068]

According to the present invention, a photosensitive composition which can be developed with an alkali aqueous solution and has excellent photosensitivity and resolution is provided, and the photosensitive composition of the present invention is cured by heating. A good polyimide film pattern having excellent heat resistance can be obtained.

Claims (3)

[Claims] (A) 100 parts by weight of a polyamic acid derivative having a structural unit represented by the following general formula (1): (Wherein, R ^{1 is a} tetravalent organic group, R ^{2 is} a divalent organic group,
R ³ and R ^{4 each represents a} monovalent organic group or a hydroxyl group, and at least one of them represents an organic group having at least one hydroxyl group bonded to an aromatic ring. ), (B) 0.5 to 20 parts by weight of a compound capable of generating an acid upon irradiation, and (C) 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. A photosensitive composition comprising 3 to 40 parts by weight. (A) 100 parts by weight of a mixture of a polyamic acid derivative having a structural unit represented by the following general formula (1) and a polyamic acid having a structural unit represented by the following general formula (2): 2] (Wherein, R ^{1 is a} tetravalent organic group, R ^{2 is} a divalent organic group,
R ³ and R ^{4 each represents a} monovalent organic group or a hydroxyl group, and at least one of them represents an organic group having at least one hydroxyl group bonded to an aromatic ring. ), Embedded image (In the formula, R ⁵ represents a tetravalent organic group, and R ⁶ represents a divalent organic group.) (B) Compounds 0.5 to 2 which generate an acid upon irradiation with radiation
A photosensitive composition comprising: 0 parts by weight; and 3 to 40 parts by weight of 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 (C). Stuff. (A) 100 parts by weight of a polyamic acid derivative having a copolymer structure containing structural units represented by the following general formulas (1) and (2): (Wherein, R ^{1 is a} tetravalent organic group, R ^{2 is} a divalent organic group,
R ³ and R ^{4 each represents a} monovalent organic group or a hydroxyl group, and at least one of them represents an organic group having at least one hydroxyl group bonded to an aromatic ring. ), Embedded image (In the formula, R ⁵ represents a tetravalent organic group, and R ⁶ represents a divalent organic group.) (B) Compounds 0.5 to 2 which generate an acid upon irradiation with radiation
A photosensitive composition comprising: 0 parts by weight; and 3 to 40 parts by weight of 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 (C). Stuff.