JP2003015293A - Photosensitive resin composition, method for producing pattern using the same and electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition suitable for use as a material of protective films and insulating films of electronic parts which cannot be subjected to high temperature treatment and electronic parts which require alkali resistance and to provide a method for producing a pattern using the composition and electronic parts. SOLUTION: The photosensitive resin composition contains a polyamide resin having repeating units of formula (I) (where X is a trivalent organic group having an aromatic ring; Y is a divalent organic group having an aromatic ring; and R1 is a monovalent organic group having a photosensitive group), photopolymerizable unsaturated monomers including a monomer having five or more photopolymerizable unsaturated bonds in one molecule and a photopolymerization initiator.

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 having excellent alkali resistance, a pattern manufacturing method using the same, and an electronic component.

[0002]

2. Description of the Related Art In recent years, polyamide and polyimide have been used as protective films and insulating films used in electronic parts.
However, the process of forming a pattern on these films includes the steps of forming a resist material on the film surface, exposing a predetermined portion, developing, removing unnecessary portions by etching, peeling the resist material, cleaning the substrate surface, etc. It is complicated. Therefore, it is desired to develop a photosensitive material in which a resist having a pattern formed by exposure and development can be used as it is as a protective film or an insulating film.

Photosensitive polyimide has been developed and is widely used as a protective film and an insulating film used in semiconductor devices. However, many photosensitive polyimides need to be imidized at a temperature of about 300 ° C. after forming a pattern, and cannot be applied to electronic parts that cannot be subjected to high temperature treatment. Further, the alkali resistance of the photosensitive polyimide is not sufficient as a protective film or an insulating film for a special electronic component requiring alkali resistance.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a photosensitive resin composition suitable as a material for a protective film or an insulating film for electronic parts which cannot be subjected to high-temperature treatment or for electronic parts which require alkali resistance, and uses the same. The present invention provides a conventional pattern manufacturing method and an electronic component.

[0005]

The present invention relates to the following photosensitive resin composition, a pattern manufacturing method using the same and an electronic component. (1) General formula (I)

[Chemical 3] (In the formula, X represents a trivalent organic group having an aromatic ring, Y represents a divalent organic group having an aromatic ring, and R1 represents a monovalent organic group having a photosensitive group). A photosensitive resin composition comprising a polyamide resin having a repeating unit, a photopolymerizable unsaturated monomer containing a monomer having 5 or more photopolymerizable unsaturated bonds in the molecule, and a photopolymerization initiator.

(2) The polyamide resin comprises a repeating unit represented by the general formula (I) and a general formula (II).

[Chemical 4] (Wherein Y and Z represent a divalent organic group having an aromatic ring), the photosensitive resin composition according to (1) above.

(3) The repeating unit represented by the general formula (I) / the repeating unit represented by the general formula (II) is 20/8.
The photosensitive resin composition according to (2) above, which has a ratio of 0 to 90/10 (molar ratio). (4) The photosensitive resin composition according to (1) or (2) above, wherein the polyamide resin has a weight average molecular weight of 8,000 to 200,000.

(5) The photosensitive resin as described in (1), (2), (3) or (4) above, wherein the photopolymerizable unsaturated monomer is 1 to 500 parts by weight with respect to 100 parts by weight of the polyamide resin. Composition. (6) 1 to 80 parts by weight of the photopolymerization initiator with respect to 100 parts by weight of the polyamide resin.
The photosensitive resin composition according to any one of (5).

(7) Pattern production including a pattern forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to any one of (1) to (6), exposing and developing through a mask Law. (8) An electronic component having a layer formed using the photosensitive resin composition according to any one of (1) to (6).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide resin used in the present invention is a compound having a repeating unit represented by the general formula (I). Those having a repeating unit represented by the general formula (II) together with the repeating unit of the general formula (I) are preferable. General formula (I) / general formula (II) is 2
The ratio is preferably 0/80 to 90/10 (molar ratio), more preferably 30/70 to 85/15 (molar ratio). When the ratio of the general formula (I) / the general formula (II) is smaller than 20/80, the ratio of the photosensitive group in the resin decreases, so that the sensitivity tends to decrease and the photosensitive property tends to deteriorate. If it is larger than / 10, gelation tends to occur, and thus the polyamide resin tends to be difficult to synthesize.

X in the above general formula (I) is a trivalent organic group containing an aromatic ring, which is generally an aromatic diamine residue capable of reacting with a dicarboxylic acid or its derivative to form an amide. Examples of the aromatic ring include a benzene ring and a naphthalene ring, and the total number of carbon atoms contained in X is preferably 6 to 40. Further, it is preferable that all three binding sites are present on the aromatic ring. Specifically, a benzene ring, a naphthalene ring, an anthracene ring, and 2 to 6 aromatic rings thereof are single bonds, oxygen atoms, sulfur atoms, sulfonyl groups, sulfinyl groups, methylene groups, 2,2-propylene groups, carbonyl groups. Groups, groups bonded through a dimethylsilyl group, a siloxane structure, etc., with 1 carbon atom on these rings
Examples thereof include groups in which the alkyl group of 4 exists as a substituent.

R1 in the above general formula (I) is a monovalent organic group having a photosensitive group, and examples of the photosensitive group include a group having a carbon-carbon double bond which is polymerizable by light,
For example, allyloxy group, acryloyloxyalkoxy group, methacryloyloxyalkoxy group, maleimidylalkoxy group, acryloyloxyalkylamino group, methacryloyloxyalkylamino group, maleimidylalkylamino group, allyl group, acryloyloxyalkyl group, methacryloyloxy group. Examples thereof include an alkyl group and an ethynyl group. Preferred are general formulas (III) to (VI)

[0013]

[Chemical 5] (In the formula, R2 represents a divalent organic group, and R3, R4, R5, R
6 and R7 are each independently a hydrogen atom or a carbon number of 1 to 4
Represents an alkyl group, a phenyl group, a vinyl group, or a propenyl group). As the divalent organic group represented by R2, an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group and a propylene group is preferable.

The above general formula (III) or general formula (IV)
Of the monovalent organic groups represented by, R2 is particularly one having 1 carbon atom.
The organic groups having an alkylene group of 4 to 4, R3 being a hydrogen atom or a methyl group, and R4 and R5 being hydrogen atoms have high sensitivity and are suitable for the photosensitive resin composition of the present invention.

In the present invention, Y and Z in the above general formulas (I) and (II) are divalent organic groups having an aromatic ring, and examples of the aromatic ring include a benzene ring and a naphthalene ring. , The total number of carbons contained in Y and Z is 6
Is preferably 40 (where Y is the general formula (I)).
Except for X-CO-R1). Also,
Both of the two binding sites are preferably present on the aromatic ring. Specifically, a benzene ring, a naphthalene ring, an anthracene ring, and 2 to 6 aromatic rings thereof are single bonds, oxygen atoms, sulfur atoms, sulfonyl groups, sulfinyl groups, methylene groups, 2,2-propylene groups, carbonyl groups. Examples thereof include a group, a dimethylsilyl group, a group bonded via a siloxane structure and the like, a group having an alkyl group having 1 to 4 carbon atoms as a substituent on these rings, and the like.

In the present invention, the method for synthesizing the polyamide resin having the repeating units represented by the general formulas (I) and (II) is, for example, the reaction of a diamine with a dicarboxylic acid or a reactive derivative of a dicarboxylic acid to form an amide. There is a method of converting into The diamine may be represented by general formula (VII) or general formula (VIII)

[Chemical 6] A diamine represented by the formula (wherein R 1, X and Z represent the above) can be used.

Examples of the diamine represented by the general formula (VII) include:

[Chemical 7] And the like, which are preferably used. Also, two or more of these may be used in combination.

As the diamine of the general formula (VIII),
For example, phenylenediamine, toluylenediamine, xylylenediamine, naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether,
4,4'-diaminobenzanilide, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenyl sulfone, 3,3 ', 5,5'-tetramethyl-4,4'-
Diaminodiphenylmethane, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 1,4-bis (4-aminocumyl) benzene, 1,
3-bis (4-aminocumyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3
-Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane,
Bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [4- (4-aminophenoxy) phenyl] ether, Bis [4- (4-amino) Examples thereof include phenoxy) phenyl] biphenyl, and these may be used in combination of two or more kinds.

The dicarboxylic acid may be represented by the general formula (I
X)

[Chemical 8] A dicarboxylic acid represented by the formula (Y represents the above) can be used.

As the dicarboxylic acid of the general formula (IX),
For example, terephthalic acid, isophthalic acid, bis (4-carboxyphenyl) ether, bis (4-carboxyphenyl) sulfone, 4,4′-biphenyldicarboxylic acid,
1,5-naphthalenedicarboxylic acid and the like can be mentioned, and these may be used in combination of two or more kinds. Of these, terephthalic acid and isophthalic acid are preferable because they are easily available and inexpensive. In particular, the use of a mixture of terephthalic acid and isophthalic acid is preferable from the viewpoint of solubility of the polyamide resin produced. The reactive derivative of the dicarboxylic acid means a dihalide of the dicarboxylic acid, for example, dichloride, dibromide, diester or the like.

In the present invention, the diamine is preferably used in a total amount of 80 to 120 mol%, and more preferably 95 to 105 mol% based on 100 mol% of the dicarboxylic acid or the reactive derivative of dicarboxylic acid. Is more preferable. If the total amount of diamine is less than 80 mol% or 120
When it is higher than the mol%, the molecular weight of the obtained resin is low and the alkali resistance and the chemical resistance tend to be poor.

The diamine represented by the above general formula (VII) is indispensable for imparting photosensitivity to the resin, and is used in an amount of 20 to 90 mol% based on 100 mol% of the total amount of diamine. Is preferable, and it is more preferable to use it so as to be 30 to 85 mol%. When it is less than 20 mol%, the ratio of the photosensitive groups in the resin is decreased, so that the sensitivity is lowered and the photosensitivity tends to be poor, and when it is more than 90 mol%, the reaction solution tends to gel and the resin Synthesis becomes difficult.

A radical polymerization inhibitor or a radical polymerization inhibitor may be added during synthesis of the polyamide resin in order to prevent dark reaction of the photosensitive group. Examples of the radical polymerization inhibitor or the radical polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone and 2,2'-methylenebis (4-ethyl-6).
-T-butylphenol), 6-t-butyl-2,3-
Xylenol, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthraquine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, cuperone, tannic acid, p- Examples thereof include benzylaminophenol, vitamin E, and nitrosamines. These may be used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or radical polymerization inhibitor used is preferably 0.01 to 20 mol% based on 100 mol% of the total amount of the diamine represented by the general formula (VII), and 0 More preferably, it is 0.05 to 10 mol%. If it is less than 0.01 mol%, the reaction solution tends to gel, and if it is more than 20 mol%, the sensitivity tends to decrease.

The organic solvent for synthesizing the polyamide resin is preferably a polar solvent in which the produced polyamide resin is completely dissolved. For example, N-methyl-2-pyrrolidone,
Examples include N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, sulfolane and the like. In addition to these polar solvents, ketones, esters, ethers, aliphatic compounds, aromatic compounds, and halides thereof can also be used, for example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl. Ketone, cyclohexanone, ethyl acetate, butyl acetate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, chlorobenzene, hexane, heptane, octane, toluene,
Xylene etc. are mentioned. These organic solvents may be used alone or in combination of two or more. The polyamide resin synthesized as described above may be used as it is as a reaction solution, or may be used after being purified by pouring the reaction solution into a poor solvent to precipitate the resin.

In the present invention, as the photopolymerizable unsaturated monomer, a monomer having 5 or more photopolymerizable unsaturated bonds in the molecule is used as an essential component. Thereby, in addition to the photosensitive characteristics of the photosensitive resin composition of the present invention, solvent resistance,
In particular, alkali resistance can be greatly improved. Further, when a photopolymerizable unsaturated monomer other than the above-mentioned monomers is used in combination, it is preferable to use a monomer having two or more photopolymerizable unsaturated bonds in the molecule in combination from the viewpoint of photosensitivity and the like. The blending amount of the photopolymerizable unsaturated monomer is preferably 1 to 500 parts by weight, more preferably 3 to 300 parts by weight, based on 100 parts by weight of the polyamide resin. 1
If the amount is less than 500 parts by weight, the density of the photosensitive group tends to be low, so that the sensitivity tends to decrease. If the amount is more than 500 parts by weight,
Since the density of the photosensitive group becomes too high, gelation is likely to occur due to a dark reaction, and storage stability tends to be poor.

Further, in 100% by weight of the photopolymerizable unsaturated monomer, 30 to 100% by weight of a monomer having 5 or more photopolymerizable unsaturated bonds in the molecule is preferably contained, and 50 to 100% by weight is contained. More preferably.
If it is less than 30% by weight, the crosslink density tends to be low and the alkali resistance tends to be poor.

The monomer having two or more photopolymerizable unsaturated bonds in the molecule is not particularly limited, and 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 trimethacrylate, 1,
4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, penta Erythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate,
Divinylbenzene, 1,3-acryloyloxy-2-
Hydroxypropane, 1,3-methacryloyloxy-
2-hydroxypropane, methylenebisacrylamide, glycerol dimethacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, tris (methacryloxyethyl) isocyanate Nurate, general formula (X)

[0029]

[Chemical 9] (In the formula, R8 represents an ethylene group or a propylene group, and R9
Represents a methyl group or a hydrogen atom, and m and n each independently represent an integer of 1 to 20) diacrylate and dimethacrylate of alkylene oxide adduct of bisphenol A represented by the general formula (XI).

[0030]

[Chemical 10] (In the formula, R10 represents a methyl group or a hydrogen atom, and m and n
Each independently represent an integer of 1 to 10) diacrylate and dimethacrylate of bisphenol A epichlorohydrin modified product, bisphenol A dimethacrylate, bisphenol A diacrylate, general formula (XII)

[0031]

[Chemical 11] (In the formula, R11 represents an ethylene group or a propylene group,
12 represents a methyl group or a hydrogen atom, and m and n each independently represent an integer of 1 to 20) diacrylate and dimethacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula (XIII)

[0032]

[Chemical 12] (In the formula, R13 represents a methyl group or a hydrogen atom, and m and n
Each independently represents an integer of 1 to 10) diacrylate and dimethacrylate of an epichlorohydrin-modified product of phthalic acid represented by the general formula (XIV)

[0033]

[Chemical 13] (In the formula, R14 represents a methyl group or a hydrogen atom, and m and n
Each independently represent an integer of 1 to 20) diacrylate and dimethacrylate of 1,6-hexanediol modified epichlorohydrin represented by the general formula (X
V)

[0034]

[Chemical 14] (In the formula, R15 represents an ethylene group or a propylene group,
16 represents a methyl group or a hydrogen atom, and 3 m's each independently represent an integer of 1 to 20) triacrylate and trimethacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula (XVI)

[0035]

[Chemical 15] (In the formula, R17 represents an ethylene group or a propylene group,
18 represents a methyl group or a hydrogen atom, and l, m and n each independently represent an integer of 1 to 20) represented by the following formula: triacrylate and trimethacrylate of alkylene oxide adduct of trimethylolpropane, a general formula ( XVI
I)

[0036]

[Chemical 16] (In the formula, R19 represents a divalent alkyl group having 1 to 5 carbon atoms, and R20 represents a methyl group or a hydrogen atom) Hexaacrylate and hexamethacrylate having a phosphazene skeleton represented by the general formula (XVIII)

[0037]

[Chemical 17] (In the formula, R21 represents an ethylene group or a propylene group,
22 and R23 are each independently a hydrogen atom or a carbon number of 1 to
4 represents an alkyl group, a phenyl group, a vinyl group or a propenyl group, and m and n each independently represent an integer of 1 to 20), a bismaleimide of an alkylene oxide adduct of bisphenol A represented by the general formula ( XIX)

[0038]

[Chemical 18] (In the formula, R24 and R25 are each independently a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group or a propenyl group, and m and n are each independently 1 to
Bismaleimide of the modified product of bisphenol A epichlorohydrin represented by the general formula (X
X))

[0039]

[Chemical 19] (In the formula, R26 and R27 are each independently a hydrogen atom,
A alkanediol bismaleimide represented by an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group or a propenyl group, and m represents an integer of 2 to 20, a general formula (X
XI)

[0040]

[Chemical 20] (In the formula, R28 and R29 are each independently a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, a vinyl group or a propenyl group, and m and n are each independently 1 to
Bismaleimide of epichlorohydrin modified product of 1,6-hexanediol represented by
2'-bis (p-maleimidylphenoxyphenyl) propane and the like can be mentioned. These monomers may be used alone or in combination of two or more.

The monomer having 5 or more photopolymerizable unsaturated bonds in the molecule is preferably a monomer having 5 or more acryloyl groups or methacryloyl groups in the molecule, particularly preferably dipentaerythritol pentaacrylate or dipentaerythritol pentaacrylate. Pentaerythritol hexaacrylate, general formula (XXII)

[0042]

[Chemical 21] (In the formula, R30 represents an acryloyl group or a methacryloyl group, R31 represents an acryloyl group, a methacryloyl group or a hydrogen atom, n represents an integer of 3 to 10, f, g,
h, i, j and k each independently represent an integer of 0 to 5) hexalactone, hexamethacrylate, pentaacrylate and pentamethacrylate of a lactone-modified dipentaerythritol represented by the general formula (X
XIII)

[0043]

[Chemical formula 22] (In the formula, R32 represents an ethylene group or a propylene group,
33 represents an acryloyl group or a methacryloyl group, R34
Represents an acryloyl group, a methacryloyl group or a hydrogen atom, and f, g, h, i, j and k are each independently 0 to 5
The hexaalkylene, hexamethacrylate, pentaacrylate and pentamethacrylate of the alkylene oxide adduct of dipentaerythritol represented by These monomers may be used alone or in combination of two or more.

In the present invention, the compounding amount of the photopolymerization initiator is preferably 1 to 80 parts by weight, and more preferably 3 to 50 parts by weight, based on 100 parts by weight of the polyamide resin. If the amount is less than 1 part by weight, the sensitivity is lowered and it becomes difficult to form a pattern. If the amount is more than 80 parts by weight, the adhesion tends to be lowered.

The photopolymerization initiator is not particularly limited, and examples thereof include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone and 4-methoxy-.
4'-dimethylaminobenzophenone, benzyl, 2,
2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone,
1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, t-butylanthraquinone, 1
-Chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10
-Phenanthraquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-
Diphenyl imidazole dimer etc. are mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention generally contains a solvent. The solvent is not particularly limited, for example, acetone, methyl ethyl ketone, cyclopentanone, a ketone compound such as cyclohexanone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, 3-methyl-3. -Methoxybutyl acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Recall monomethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol -t- butyl ether acetate, triethylene glycol dimethyl ether,
Triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate,
Triethylene glycol butyl ether acetate, alkylene glycol ether compounds such as triethylene glycol-t-butyl ether acetate, alcohol compounds such as methanol, ethanol, propyl alcohol, butyl alcohol, hexane, heptane, aliphatic compounds such as octane, chloroform, dichloromethane,
1,2-Dichloroethane, chlorobenzene and other aliphatic compounds and aromatic compound halides, ethyl acetate, butyl acetate and other ester compounds, ethyl ether, tetrahydrofuran, dioxane and other ether compounds, benzene, toluene, xylene and other aromatic compounds Compound, N, N-dimethylacetamide, N, N-dimethylformamide,
Examples of the organic solvent include amide compounds such as N-hydroxymethyl-2-pyrrolidone, γ-butyrolactone, N-methyl-2-pyrrolidone, aprotic polar solvents such as sulfolane and dimethyl sulfoxide. These organic solvents may be used alone or in combination of two or more.

A radical polymerization inhibitor or a radical polymerization inhibitor may be added to the photosensitive resin composition of the present invention in order to enhance storage stability. Examples of the radical polymerization inhibitor or the radical polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, 2,2′-methylenebis (4-ethyl-6-t).
-Butylphenol), 6-t-butyl-2,3-xylenol, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene,
Examples thereof include m-dinitrobenzene, phenanthraquine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, cuperone, tannic acid, p-benzylaminophenol, vitamin E and nitrosamines. These may be used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or radical polymerization inhibitor used is such that the polyamide resin having the repeating units represented by the general formulas (I) and (II) and the photopolymerizable unsaturated bond are contained in the molecule. The amount is preferably 0.01 to 30 parts by weight, and more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the total amount of the two or more monomers. If it is less than 0.01 part by weight, the stability of the photosensitive resin composition tends to decrease, and if it exceeds 30 parts by weight, the sensitivity tends to decrease.

The photosensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer, a metal substrate or a ceramic substrate by a method such as a dipping method, a spray method, a screen printing method or a spin coating method, and a solvent is heated. By removing it, a coating film made of a non-volatile component of the photosensitive resin composition of the present invention can be formed. The film thickness of this coating film is not particularly limited, but from the viewpoint of developability and the like, it is preferably 1 to 50 μm, more preferably 2 to 40 μm, and 2 to 3
Particularly preferably, it is 0 μm. The method for producing a pattern of the present invention is such that the coating film is exposed to a pattern by irradiating with actinic rays or actinic rays through a mask in which a desired pattern is drawn, and then the unexposed portion is treated with a suitable developing solution. By developing and removing with, a coating film having a desired pattern is obtained.

As the developing solution, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-
Methyl-2-pyrrolidone, γ-butyrolactone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, a good solvent such as dimethylsulfoxide, a mixed solution of the good solvent and a lower solvent such as a lower alcohol, ketone, water, an aliphatic compound or an aromatic compound. Is mentioned. After development, if necessary, rinse with water or a poor solvent and drying at about 180 ° C. to obtain a coating film of the photosensitive resin composition of the present invention having a desired pattern. The coating film formed from the photosensitive resin composition of the present invention thus obtained is a surface protective film or interlayer such as a junction coat film, a buffer coat film or an alpha ray shielding film used for electronic parts such as semiconductor elements. Used for forming an insulating film.

The electronic component of the present invention has a coating film made of the photosensitive resin composition of the present invention having a desired pattern as the surface protective film or the interlayer insulating film, but other than that, there is no particular limitation, and various types are used. It can have various structures.

[0052]

The present invention will be described in more detail with reference to the following examples. Example 1 In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube and a calcium chloride tube, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP). 30.6 g, 4,4'-
Diaminodiphenyl ether (hereinafter abbreviated as DDE)
1.7 g, 3,5-diaminobenzoic acid 2-methacryloyloxyethyl ester 21.9 g, 2,2'-
3.3 g of methylenebis (4-ethyl-6-t-butylphenol), N-methyl-2-pyrrolidone (hereinafter N
(Abbreviated as MP) 419.8 g, and under a nitrogen atmosphere,
Cooled to 0 ° C. with stirring. After adding 27.8 g of propylene oxide, add 1 part of isophthalic acid chloride.
6.2 g, 16.2 g of terephthaloyl chloride were added,
The reaction was allowed to stir at room temperature for 1 hour. The obtained reaction solution was poured into water, pulverized with a mixer, washed with water, and then dried to obtain a polyamide resin powder having a general formula (I) / general formula (II) of 50/50 (molar ratio). Got The obtained polyamide resin powder was subjected to gel permeation chromatography (hereinafter, abbreviated as GPC; eluent was 0.05 mol / L NMP phosphate solution, liquid velocity was 1 ml / min, and detection was UV detector (250 nm)). When measured, the weight average molecular weight was 150,000 in terms of polystyrene.

To 2.179 g of this polyamide resin powder,
As the photopolymerizable unsaturated monomer, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, which are monomers having 5 or more photopolymerizable unsaturated bonds in the molecule (KA manufactured by Nippon Kayaku Co., Ltd.).
YARAD DPHA; hereinafter abbreviated as DPHA) 2.6
88 g, 1.0 of benzophenone as a photopolymerization initiator
16 g, 0.335 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, 12.53 g of diethylene glycol dimethyl ether (hereinafter abbreviated as DMDG) as an organic solvent, and 12.53 g of NMP were added and mixed to give the present invention. To obtain a photosensitive resin composition.

This photosensitive resin composition was applied onto a 5-inch silicon wafer (surface: Si) by spin coating,
A coating film was formed by heating and drying at 90 ° C. for 3 minutes. The obtained coating film was imagewise exposed to 1000 mJ / cm ² through a negative mask with an ultrahigh pressure mercury lamp, and then developed with triethylene glycol dimethyl ether / butyl cellosolve acetate (60/40) (weight ratio). The coating film was washed with water and then dried in a dryer at 180 ° C. for 1 hour to obtain a coating film having a pattern and a thickness of 3.2 μm, which was obtained by using the photosensitive resin composition of the present invention.

Example 2 2.179 g of the polyamide resin powder obtained in Example 1
In addition, trimethylolpropane trimethacrylate (NK ester TMPT manufactured by Shin-Nakamura Chemical Co., Ltd .; hereinafter abbreviated as TMPT), which is a monomer having three or more photopolymerizable unsaturated bonds in the molecule, is used as the photopolymerizable unsaturated monomer. 0.538 g, DPHA which is a monomer having 5 or more photopolymerizable unsaturated bonds in the molecule is 2.150 g, and benzophenone is 1.016 g, N, as a photopolymerization initiator.
0.335 g of N'-tetraethyl-4,4'-diaminobenzophenone, DMDG as an organic solvent 12.
53 g and 12.53 g of NMP were added and mixed to obtain a photosensitive resin composition of the present invention. Using this photosensitive resin composition and performing the same operation as in Example 1, the film thickness having a pattern obtained by using the photosensitive resin composition of the present invention was 3.0.
A coating film of μm was obtained.

Example 3 2.179 g of the polyamide resin powder obtained in Example 1
In addition, as a photopolymerizable unsaturated monomer, TMPT 1.3
44 g, DPHA 1.344 g, benzophenone 1.016 g, N, N′-tetraethyl-4,4′-diaminobenzophenone 0.33 as a photopolymerization initiator
5g, as organic solvent, DMDG 12.53g, NM
12.53 g of P was added and mixed to obtain a photosensitive resin composition of the present invention. Example 1 using this photosensitive resin composition
By the same operation as above, a coating film having a pattern and a film thickness of 2.8 μm, which was obtained by using the photosensitive resin composition of the present invention, was obtained.

Example 4 2.179 g of the polyamide resin powder obtained in Example 1
In addition, as a photopolymerizable unsaturated monomer, DPHA was added to 0.6
23 g, benzophenone 0.2 as a photopolymerization initiator
34 g, 0.077 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, DM as an organic solvent
6.22 g of DG and 6.22 g of NMP were added and mixed,
The photosensitive resin composition of the present invention was obtained. Using this photosensitive resin composition, a coating film having a pattern and a film thickness of 3.0 μm, which was obtained by using the photosensitive resin composition of the present invention, was obtained by the same operation as in Example 1.

Example 5 2.179 g of the polyamide resin powder obtained in Example 1
In addition, DPHA as a photopolymerizable unsaturated monomer is 0.1
29 g, 0.1% benzophenone as a photopolymerization initiator
93 g, N, N'-tetraethyl-4,4'-diaminobenzophenone 0.064 g, DM as an organic solvent
6.73 g of DG and 6.73 g of NMP were added and mixed,
The photosensitive resin composition of the present invention was obtained. Using this photosensitive resin composition, a coating film having a film thickness of 2.5 μm having a pattern obtained by using the photosensitive resin composition of the present invention was obtained by the same operation as in Example 1.

Example 6 BAPP (12.3 g), DDE (0.7 g), 3,5-diaminobenzoic acid 2-methacryloyloxyethyl ester (35.0 g), and 2,2'-methylenebis (4-ethyl-6-t). -Butylphenol) and NMP (381.5 g) were used, and the same operation as in Example 1 was carried out to obtain a polyamide resin having a general formula (I) / general formula (II) of 80/20 (molar ratio). Of powder was obtained. The obtained polyamide resin powder is GPC (eluent is 0.05 mol / L
The NMP phosphate solution, the liquid velocity was 1 ml / min, and the detection was carried out using a UV detector (250 nm). The weight average molecular weight was 107,000 in terms of polystyrene. The same operation as in Example 4 was performed except that the obtained polyamide resin was used to obtain a photosensitive resin composition of the present invention.
Using this photosensitive resin composition, a coating having a pattern and a film thickness of 2.6 μm, which was obtained by using the photosensitive resin composition of the present invention, was obtained by the same operation as in Example 1.

Example 7 BAPP 42.9 g, DDE 2.3 g, 3,5-diaminobenzoic acid 2-methacryloyloxyethyl ester 13.1 g, 2,2'-methylenebis (4-ethyl-6-t) -Butylphenol) and 2.05 g of NMP and 445.2 g of NMP were used, and the same operation as in Example 1 was carried out to obtain a polyamide resin having a general formula (I) / general formula (II) of 30/70 (molar ratio). Of powder was obtained. The obtained polyamide resin powder is GPC (eluent is 0.05 mol / L
The weight average molecular weight was 98,000 in terms of polystyrene when measured with a phosphoric acid NMP solution, the liquid velocity was 1 ml / min, and the detection was performed using a UV detector (250 nm).
The same operation as in Example 4 was carried out except that the obtained polyamide resin was used to prepare a photosensitive liquid composed of the photosensitive resin composition of the present invention. Using this photosensitive liquid, the same operation as in Example 1 was carried out to obtain a coating film having a pattern of the photosensitive resin composition of the present invention and having a film thickness of 3.0 μm.

Comparative Example 1 BAPP (6) was placed in a 500 ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a calcium chloride tube.
1.2 g, DDE 3.3 g and NMP 483.5 g were added, and it cooled to 0 degreeC, stirring under nitrogen atmosphere. After adding 27.8 g of propylene oxide, 16.2 g of isophthalic acid chloride and 16.2 g of terephthalic acid chloride were added and reacted at room temperature for 1 hour with stirring. The obtained reaction solution was poured into water, which was crushed with a mixer,
After being washed with water and dried, the general formula (I) / the general formula (II)
A polyamide resin powder having a ratio of 0/100 (molar ratio) was obtained. The obtained polyamide resin powder is GPC (eluent is 0.05 mol / L NMP phosphate solution, liquid speed is 1 ml
/ Min, detection was performed using a UV detector (250 nm)), and the weight average molecular weight was 10 in terms of polystyrene.
It was 2,000. The same operation as in Example 1 was carried out except that the obtained polyamide resin was used to prepare a photosensitive resin composition. Example 1 using this photosensitive resin composition
A coating film was formed, exposed and developed by the same operation as in 1. However, a coating film having a pattern was not obtained.

Comparative Example 2 2.179 g of the polyamide resin powder obtained in Example 1
And 2.6 as the photopolymerizable unsaturated monomer, TMPT.
88 g, 1.0 of benzophenone as a photopolymerization initiator
16 g, 0.335 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, DM as an organic solvent
12.53 g of DG and 12.53 g of NMP were added and mixed to obtain a photosensitive resin composition. Using this photosensitive resin composition, a coating film having a pattern and a film thickness of 3.0 μm was obtained by the same operation as in Example 1.

Table 1 shows the compounding amounts of the resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2, and the weight average molecular weight of the polyamide resin. In the table, the monomer means a monomer having two or more photopolymerizable unsaturated bonds in the molecule. The pentafunctional or higher functional monomer means a monomer having 5 or more photopolymerizable unsaturated bonds in the molecule, and the ratio thereof is a ratio to 100% by weight of a monomer having 2 or more photopolymerizable unsaturated bonds in the molecule. . Moreover, the compounding quantity shows the compounding quantity with respect to 100 parts by weight of the total amount of the polyamide resin.

[0064]

[Table 1]

Table 2 shows the evaluation results of the coating films produced in Examples 1-7 and Comparative Examples 1-2.

[Table 2]

In Examples 1 to 7, since the photosensitive resin composition specified in the present invention was used, the alkali resistance was excellent.
A coating film having a pattern was obtained. In Comparative Example 1, since the polyamide resin not having the resin structure defined in the present invention was used, the photosensitive property was inferior and the coating film having the pattern could not be obtained. In Comparative Example 2, since the monomer having 5 or more photopolymerizable unsaturated bonds defined in the present invention was not used, the alkali resistance was poor, and the coating film was peeled off after PCT.

[0067]

As described above, the photosensitive resin composition of the present invention can form a coating film having a pattern excellent in heat resistance and alkali resistance without requiring high temperature treatment, It can be suitably used as a material for a protective film or an insulating film used for electronic parts that cannot be subjected to high temperature treatment or electronic parts that require alkali resistance.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

1 ... Semiconductor substrate 2 ... Protective film 3 ... First conductor layer 4 ... Interlayer insulating film layer 5 ... Photosensitive resin layer 6A, 6B, 6C ... windows 7 ... Second conductor layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 21/312 H01L 21/30 502R F term (reference) 2H025 AA01 AA08 AA10 AA20 AB16 AB17 AC01 AD01 BC13 BC42 BC68 BC82 BC92 CA00 FA17 FA29 4J011 CA08 CB03 CC10 PA27 PA43 PA45 PA96 PB30 PC02 QA12 QA13 QA17 QA19 QA23 SA04 SA15 SA16 SA22 SA34 SA42 SA54 SA62 SA63 SA64 SA78 4J026 AB29 BA07 BA28 BA29 DB06 DB36 FA05 5F058 AA10 AA10 AA10

Claims (8)

[Claims] 1. A compound represented by the general formula (I): (In the formula, X represents a trivalent organic group having an aromatic ring, Y represents a divalent organic group having an aromatic ring, and R1 represents a monovalent organic group having a photosensitive group). A photosensitive resin composition comprising a polyamide resin having a repeating unit, a photopolymerizable unsaturated monomer containing a monomer having 5 or more photopolymerizable unsaturated bonds in the molecule, and a photopolymerization initiator. 2. The polyamide resin is represented by the general formula (I) or the general formula (II): The photosensitive resin composition according to claim 1, which has a repeating unit represented by the formula (wherein Y and Z represent a divalent organic group having an aromatic ring). 3. A repeating unit represented by the general formula (I):
The repeating unit represented by the general formula (II) is 20/80 to
The photosensitive resin composition according to claim 2, which has a ratio of 90/10 (molar ratio). 4. The weight average molecular weight of the polyamide resin is
It is 8,000 to 200,000.
The photosensitive resin composition described. 5. The photosensitive resin composition according to claim 1, wherein the photopolymerizable unsaturated monomer is 1 to 500 parts by weight with respect to 100 parts by weight of the polyamide resin. 6. With respect to 100 parts by weight of the polyamide resin,
The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is 1 to 80 parts by weight. 7. A pattern manufacturing method comprising a pattern forming step of forming a photosensitive layer on a substrate using the photosensitive resin composition according to claim 1 and exposing and developing through a mask. 8. An electronic component having a layer formed by using the photosensitive resin composition according to claim 1.