JP2003084434A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having such photosensitivity as to simultaneously exhibit high sensitivity and high resolution and containing a polyimide having high heat resistance, a low dielectric constant, low stress, mechanical stability, a low coefficient of linear expansion, low hygroscopicity, adhesiveness and very high solvent solubility and to provide a method for producing a relief pattern using the polyimide-containing positive photosensitive resin composition. SOLUTION: The positive photosensitive resin composition contains (a) a polyimide having repeating units of formula (I) and (b) a photosensitive agent. The method for producing a relief pattern comprises a step for applying and drying the positive photosensitive resin composition on a supporting substrate and successive steps for exposing, developing and heating the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel positive photosensitive resin composition. More specifically, it has photosensitivity capable of simultaneously expressing high sensitivity and high resolution, and has high heat resistance, low dielectric constant, low stress, mechanical stability, low linear expansion coefficient, low hygroscopicity, adhesiveness, And a positive photosensitive resin composition comprising a polyimide having extremely high solvent solubility, and a method for producing a relief pattern using the positive photosensitive resin composition.

[0002]

2. Description of the Related Art Inorganic substances have been used in the past for photosensitive materials having excellent heat resistance, particularly for insulating layers and protective layers of solid-state elements in the semiconductor industry. In recent years, movements such as high integration, high density, high reliability, and high speed of electronic devices have rapidly spread, and as a new insulating material replacing conventional inorganic materials,
High heat resistant resins such as polyimide are in the spotlight. Polyimide not only has heat resistance above 300 ° C and excellent mechanical properties, but also has excellent electrical properties such as low dielectric constant and high insulation. Furthermore, polyimide is superior to inorganic materials in terms of flattening ability and workability.

Conventionally, polyimide has mainly used polyamic acid as its precursor, but its storage stability is extremely low,
It was a big inconvenience to use. For forming a positive pattern using soluble polyimide, see WO 9
9/19771. The polyimide-soluble solvents mentioned here are limited to some polar solvents such as N-methyl-2-pyrrolidone and dimethylacetamide, and other solvents having better coating properties can be used as resin compositions. The desire to use it as a solvent for products has not been met at all.

[0004]

One of the problems to be solved by the present invention is to have photosensitivity capable of simultaneously exhibiting high sensitivity and high resolution, and having high heat resistance, low dielectric constant, low stress, It is an object of the present invention to provide a positive photosensitive resin composition containing a polyimide having mechanical stability, low linear expansion coefficient, low hygroscopicity, adhesiveness, and extremely high solvent solubility.

Another of the problems to be solved by the present invention is photosensitivity capable of simultaneously exhibiting high sensitivity and high resolution, and also high heat resistance, low dielectric constant, low stress and mechanical stability. ,
It is an object of the present invention to provide a method for producing a relief pattern using a positive photosensitive resin composition containing a polyimide having a low coefficient of linear expansion, low hygroscopicity, adhesiveness, and extremely high solvent solubility.

[0006]

As a result of intensive studies, the inventors of the present invention have photosensitivity capable of simultaneously exhibiting high sensitivity and high resolution, and have high heat resistance, low dielectric constant, low stress, A polyimide having mechanical stability, low linear expansion coefficient, low hygroscopicity, adhesiveness, and extremely high solvent solubility was found, and the positive photosensitive resin composition of the present invention was completed.

That is, the present invention is specified by the matters described in [1] to [6] below.

[1] (a) General formula (I) (Chemical formula 4)

[0009]

[Chemical 4]

(In the formula, n is a rational number within the range of 0 <n <100 and represents a copolymerization ratio in the resin. R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom number 1 to 20 represents an alkyl group, R ₃ represents a divalent organic group that imparts an alkali-soluble function to a resin, Z represents a tetravalent aromatic group, and a polyimide having a repeating unit represented by the following formula: (b) A positive photosensitive resin composition containing a photosensitizer.

[2] The positive photosensitive resin composition as described in [1], wherein in the general formula (I), R ₃ is a divalent organic group having at least one carboxyl group or hydroxyl group.

[3] In the general formula (I), Z is the following formula (Formula 5).

[0013]

[Chemical 5]

(In the formula, W is a direct bond, -CH2-, -O-,
It represents a group selected from the group consisting of -SO2-, -S-, -CO-, -C (= N2)-, an isopropylidene group, and a hexafluorinated isopropylidene group. r are each independently
It represents an alkyl group having 1 to 4 carbon atoms, a halogen group, a phenyl group or a hydrogen atom. a represents the integer of 1-3. )
The positive photosensitive resin composition according to [1] or [2], which is selected from

[4] (b) The photosensitizer is a 1,2-naphthoquinonediazide-4-sulfonic acid ester compound and / or a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound. The positive photosensitive resin composition according to any one of [1] to [3].

The photosensitizer of [5] (b) is 1,
A positive photosensitive resin composition according to [4], which is selected from a 2-naphthoquinonediazide-4-sulfonic acid ester compound and / or a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound. .

[0017]

[Chemical 6]

[6] A relief pattern including the steps of coating and drying the positive photosensitive resin composition of [1] to [5] on a supporting substrate, exposing, developing and heat treating. Production method. In the present invention, by using a solvent-soluble polyimide as the resin used in the resin composition, the storage stability, which has been a problem with conventional polyamic acids, is significantly improved. Furthermore, since it is not necessary to imidize the polyamic acid in the post-baking step during the production of a relief pattern using this resin composition, low-temperature drying is possible and the productivity is greatly improved.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The positive photosensitive resin composition of the present invention comprises (a) the general formula (I)

[0020]

[Chemical 7]

(In the formula, n is a rational number in the range of 0 <n <100 and represents a copolymerization ratio in the resin. R ₁ and R ₂ are each independently a hydrogen atom or a carbon atom of 1 to 1). 20 represents an alkyl group, R ₃ represents a divalent organic group that imparts an alkali-soluble function to a resin, Z represents a tetravalent aromatic group, and a polyimide having a repeating unit represented by the following formula: (b) It is characterized by containing a photosensitizer.

N in the formula (I) is not particularly limited as long as it is a rational number within the range of 0 <n <100, but preferably 10
To 90, more preferably 20 to 80. this
n does not represent the actual number of repeats but represents a ratio, and the resin of the present invention is a random copolymer or a block copolymer.

R ₁ and R _{2 in} formula (I) are not particularly limited as long as they are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. As the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, isopropyl group, t-
Examples thereof include a butyl group. The sites of R ₁ and R _{2 on} the 1,1-dimethylindane skeleton are not particularly limited.
R ₃ in the formula (I) is not particularly limited as long as it is a divalent organic group that imparts an alkali-soluble function to the resin.

A preferred form is a divalent organic group having at least one carboxyl group or hydroxyl group. More specifically, examples thereof include a benzoic acid group and a hydroxyphenylene group. Z in the formula (I) represents a tetravalent aromatic group, and the following compound (Formula 8) is preferable.

[Chemical 8] W is a direct bond, -CH _2- , -O-, -SO _2- , -S-, -C
There is no particular limitation as long as it is a group selected from the group consisting of O-, -C (= N ₂ )-, an isopropylidene group, and a hexafluorinated isopropylidene group. Examples of the alkyl group having 1 to 4 carbon atoms of r include a methyl group, an ethyl group, and an isopropyl group, and examples of the halogen group include a fluoro group and a chloro group. The method for evaluating the logarithmic viscosity of polyimide is not particularly limited, but, for example, polyimide powder 0.
After dissolving 50 g in 100 ml of N-methyl-2-pyrrolidone, it can be measured at 35 ° C.

In the present invention, the logarithmic viscosity of the polyimide is not particularly limited, but the preferable logarithmic viscosity is preferably 0.1 to 3.0, and 0.15 to 2.
5 is more preferable, and 0.2-2.0 is still more preferable.
If the logarithmic viscosity of the polyimide is too low, the film strength of the photosensitive resin composition may be lowered, or the unexposed portion may have film slippage, which may cause problems. If the logarithmic viscosity of the polyimide is too high, generally, when it is a photosensitive resin composition, the solubility of the polyimide in a solvent is reduced, and the resolution at the time of exposure is lowered, or the sensitivity is lowered and there is a problem. May be.

The polyimide contained in the positive photosensitive resin composition of the present invention has various physical properties such as various diamines and tetracarboxylic dianhydrides in addition to the repeating unit component having the structure represented by the general formula (I). For example, for the purpose of controlling heat resistance, hygroscopicity, thermal expansion coefficient, dielectric constant, refractive index, birefringence, etc., they may be copolymerized as necessary.

The polyimide contained in the positive photosensitive resin composition of the present invention may be manufactured by any method. The preferred method for producing the polyimide contained in the positive photosensitive resin composition of the present invention is a diaminoindane derivative represented by the general formula (II), a diamine represented by the general formula (III), and a general formula (IV). Is a method in which a tetracarboxylic acid dianhydride represented by

[0028]

[Chemical 9]

[0029]

[Chemical 10]

[0030]

[Chemical 11]

In the above formula, R ₁ , R ₂ , R ₃ and Z have the same meanings as described above. Examples of the diaminoindane derivative represented by the formula (II) include 5,7-diamino-1,1-dimethylindane, 4,7-diamino-1,1-dimethylindane and 5,7-diamino-1,1, 4-trimethylindan, 5,7-diamino-1,1,6-trimethylindane, 5,7-diamino-1,1-dimethyl-4-ethylindan, 5,7-diamino-1,1-dimethyl-
6-ethylindan, 5,7-diamino-1,1-dimethyl-4-isopropylindan, 5,7-diamino-
1,1-dimethyl-6-isopropylindane, 5,7
-Diamino-1,1-dimethyl-4-n-propylindane, 5,7-diamino-1,1-dimethyl-6-n-
Propylindan, 5,7-diamino-1,1-dimethyl-4-sec-butylindan, 5,7-diamino-
1,1-dimethyl-6-sec-butylindan, 5,
7-diamino-1,1-dimethyl-4-n-butylindan, 5,7-diamino-1,1-dimethyl-6-n-
Butylindan, 5,7-diamino-1,1-dimethyl-4-tert-butylindan, 5,7-diamino-
1,1-dimethyl-6-tert-butylindan,
5,7-diamino-1,1,4,6-tetramethylindane, 6,7-diamino-1,1,4,5-tetramethylindane, 4,7-diamino-1,1,5,6- Tetramethylindan, 5,7-diamino-1,1-dimethyl-4,6-diethylindane, 5,7-diamino-
1,1-dimethyl-4,6-diisopropylindane,
5,7-diamino-1,1,4-trimethyl-6-te
rt-Butylindane or the like is used.

The diamine represented by the formula (III) is, for example,
3,5-diaminobenzoic acid, 2-hydroxy-1,4-
Diaminobenzene, 3,3'-dihydroxy-4,
4'-diaminobiphenyl or the like is used. Examples of the tetracarboxylic dianhydride component represented by the formula (IV) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4. 4'-benzophenone tetracarboxylic dianhydride, bis (3,4-
Dicarboxyphenyl) ether dianhydride, bis (3,3
4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedi Anhydrous, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-
Dicarboxyphenoxy) benzene dianhydride, 4,4 '
-Bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7
-Naphthalene tetracarboxylic dianhydride, 1,4,5,
8-naphthalenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride Anhydrous, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride Substance, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (2,3-
Dicarboxyphenyl) sulfone dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy)
Benzene dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, and the like can be used alone or in combination as appropriate. In addition, for all types of tetracarboxylic dianhydride components described above, some or all of the hydrogen atoms on their aromatic rings are fluoro, methyl, methoxy, trifluoromethyl, or trifluoro. A diamine substituted with a substituent selected from a methoxy group can also be used. Furthermore, an ethynyl group serving as a crosslinking point, a benzocyclobuten-4′-yl group, a vinyl group,
An allyl group, a cyano group, an isocyanate group, and an isopropenyl group can be used even if introduced as a substituent to some or all of the hydrogen atoms on the aromatic ring of the tetracarboxylic dianhydride. Furthermore, the vinylene group, the vinylidene group, and the ethynylidene group, which are crosslinking points, can be incorporated in the main chain skeleton, not as a substituent, preferably within a range that does not impair the molding processability. Further, for the purpose of introducing a branch, a part of the tetracarboxylic acid dianhydride may be replaced with hexacarboxylic acid trianhydride or octacarboxylic acid tetraanhydride. These tetracarboxylic acid dianhydride components can be used alone or in combination, if necessary.

In producing the polyimide contained in the positive photosensitive resin composition of the present invention, the diaminoindane derivative represented by the above general formula (II), the diamine represented by the above general formula (III), and the above In addition to the tetracarboxylic acid dianhydride represented by the general formula (IV), various other diamines can be used as monomers for copolymerization.

Other diamine components used in the copolymerization are not limited, but include, for example, a) one benzene ring, p-phenylenediamine and m-phenylenediamine, and b) two benzene rings. , 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,
3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4 '
-Diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone,
3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-
Di (3-aminophenyl) propane, 2,2-di (4-
Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-
Di (3-aminophenyl) -1,1,1,3,3,3-
Hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl)- 1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1
-Phenylethane, 1- (3-aminophenyl) -1-
(4-aminophenyl) -1-phenylethane, c) 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4 having 3 benzene rings -Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl)
Benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene,
1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene,
1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-
α, α-ditrifluoromethylbenzyl) benzene,
1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-
α, α-ditrifluoromethylbenzyl) benzene,
2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine,
d) 4,4′-bis (3-having 4 benzene rings
Aminophenoxy) biphenyl, 4,4'-bis (4-
Aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-
Aminophenoxy) phenyl] sulfide, bis [4-
(4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, e) 1,3-bis [4-having 5 benzene rings
(3-Aminophenoxy) benzoyl] benzene, 1,
3-bis [4- (4-aminophenoxy) benzoyl]
Benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-
Aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α- Dimethylbenzyl] benzene,
1,4-bis [4- (3-aminophenoxy) -α, α
-Dimethylbenzyl] benzene, 1,4-bis [4-
(4-Aminophenoxy) -α, α-dimethylbenzyl] benzene, f) 4,4′-bis [4-having 6 benzene rings
(4-Aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,
4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, g) an aromatic substituent Having, 3,3′-diamino-
4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone,
3,3'-diamino-4-phenoxybenzophenone,
3,3′-diamino-4-biphenoxybenzophenone, h) 6,6′-bis (3-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1 ′ having a spirobiindane ring -Spirobiindane, 6,6'-bis (4-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, i) Siloxanediamines, 1,3-bis ( Three
-Aminopropyl) tetramethyldisiloxane, 1,3
-Bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, j) ethylene glycol diamines Bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis [2
-(Aminomethoxy) ethyl] ether, bis [2-
(2-Aminoethoxy) ethyl] ether, bis [2-
(3-Aminoprotoxy) ethyl] ether, 1,2-
Bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-
Aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, k) methylenediamine, ethylenediamine,
1,3-diaminopropane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, 12-diaminododecane, 1) alicyclic diamines, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4
-Diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4-di (2-aminoethyl)
Cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2,2
Examples include 2,1] heptane and 2,5-bis (aminomethyl) bicyclo [2,2,1] heptane.

Further, a diamine obtained by substituting a part or all of hydrogen atoms on the aromatic ring of the diamine with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group is also available. Can be used.

Further, depending on the purpose, an ethynyl group serving as a crosslinking point, a benzocyclobuten-4'-yl group, a vinyl group,
An allyl group, a cyano group, an isocyanate group, and an isopropenyl group can be used even if introduced as a substituent to some or all of the hydrogen atoms on the aromatic ring of the diamine.

Furthermore, depending on the purpose, the vinylene group, vinylidene group, and ethynylidene group, which serve as crosslinking points, may be incorporated in the main chain skeleton instead of in the substituent. Further, a part of the diamine may be replaced with triamines or tetraamines for the purpose of introducing branching. These diamines can be used alone or as a mixture, if necessary. These diamines are preferably used in an amount of 0 to 50 mol%, more preferably 0 to 30 mol%, based on the total diamine components of the raw materials used for producing the polyimide.

The polyimide contained in the positive photosensitive resin composition of the present invention can be produced without using a solvent, but it is particularly preferable to carry out the reaction in an organic solvent. Although the solvent used in this reaction is not limited, for example, (a) a phenolic solvent such as phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol. , P-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol,
3,5-xylenol, (b) aprotic amide solvent, N, N-dimethylformamide, N, N-
Dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-
2-Imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, (c) ether solvent 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2- Methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2
-Methoxyethoxy) ethyl] ether, 1,4-dioxane, (d) amine solvents such as pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ.
-Picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine,
(E) Other solvent, dimethyl sulfoxide,
Dimethyl sulfone, diphenyl ether, sulfolane,
Diphenyl sulfone, tetramethyl urea, anisole,
Water, benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene,
Brombenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methanol, ethanol, propanol, isopropanol,
Examples thereof include butanol, isobutanol, pentane, hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate and the like. These solvents may be used alone or in combination of two or more. These solvents are preferably used in an amount of 100 to 3000 parts by weight, more preferably 150 to 2000 parts by weight, based on 100 parts by weight of the polyimide produced.

In the production of the polyimide contained in the positive photosensitive resin composition of the present invention, an end capping agent can be used if necessary. The end capping agent that can be used is not particularly limited, but a typical one is a monoamine or a dicarboxylic acid anhydride.

Examples of monoamines include aniline and
o-toluidine, m-toluidine, p-toluidine,
2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-xylidine,
3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline,
m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline,
o-anisidine, m-anisidine, p-anisidine, o
-Phenetidine, m-phenetidine, p-phenetidine, o-aminophenol, m-aminophenol, p
-Aminophenol, o-aminobenzaldehyde, m
-Aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2
-Aminophenyl phenyl ether, 3-aminophenyl phenyl ether, 4-aminophenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4 -Aminophenyl phenyl sulfide, 2
-Aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-
Amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-
2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-
Aminoanthracene, 9-aminoanthracene, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dipentylamine, benzylamine , Cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine and the like.

As the dicarboxylic acid anhydride, for example, phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, 2,
3-dicarboxyphenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-
Biphenyldicarboxylic acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride 1,3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 1,2
-Anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid anhydride and the like. A part of the structure of these monoamine or dicarboxylic acid anhydride may be substituted with a group that is not reactive with the amine or dicarboxylic acid anhydride.

In the production of the polyimide of the present invention, a known catalyst can be used in combination. For example, it can be carried out in the coexistence of a base catalyst and an acid catalyst.

Examples of the base catalyst include various amine solvents described in the above item (d), organic bases such as imidazole, N, N-dimethylaniline and N, N-diethylaniline,
Examples thereof include inorganic bases represented by potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate. These base catalysts can be used alone or as a mixture, if necessary.

Examples of acid catalysts include salts of organic acids and mineral acids. More specifically, as the organic acid, crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid, etc. Examples of the salts of mineral acids include salts of mineral acids such as hydrochloric acid, phosphoric acid and nitric acid with a base such as pyridine, quinoline, triethylamine, N-methylmorpholine and trimethylenediamine. These acid catalysts can be used alone or as a mixture, if necessary. These base catalysts can be used alone or as a mixture, if necessary.

If desired, the acid catalyst and the base catalyst may be used in combination. These catalysts are 0 to 500 mol%, more preferably 0 to 400 mol% based on 100 mol% of all the diamine components of the raw materials used for the production of polyimide.
It is preferably used in mol%.

In the production of the polyimide contained in the positive photosensitive resin composition of the present invention, the polymerization temperature and the polymerization time vary depending on the presence or absence of the solvent and the catalyst to be used and the kind thereof, but are generally 25 ° C to 250 ° C. 1 to 24 hours is sufficient.

The polyimide obtained by the above method may be used as a solution in the next step of producing a resin composition. Further, this polyimide solution is poured into a poor solvent such as water, methanol or ethanol to precipitate a polymer, which is collected by filtration, washed and dried to be recovered as a solid, which is used in the next step of producing a resin composition. I don't mind.

The photosensitizer contained in the positive photosensitive resin composition of the present invention is not particularly limited, but is preferably 1,2-
A naphthoquinone diazide-4-sulfonic acid ester compound and / or a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound can be used.

Specifically, 1, represented by the following (Chemical formula 12)
A 2-naphthoquinonediazide-4-sulfonic acid ester compound and / or a 1,2-naphthoquinonediazide-5-sulfonic acid ester compound can be preferably used.

[0050]

[Chemical 12]

In the positive photosensitive resin composition of the present invention, the photosensitizer is added in an amount of 1 to 20 with respect to 100 parts by weight of the polyimide.
It is preferable to contain 0 part by weight, more preferably 1 to 100 parts by weight.

Since the polyimide contained in the positive photosensitive resin composition of the present invention has extremely high solubility in a general-purpose organic solvent, it can be easily dissolved in a general-purpose organic solvent.

The general-purpose organic solvent used here is not limited, but for example, (a) phenol-based solvents such as phenol, o-chlorophenol,
m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-
Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, (b) aprotic amide solvent, 1,3-dimethyl -2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotriamide, (c) ether solvent, 1,
2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane,
(D) Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2, which are amine solvents.
6-lutidine, trimethylamine, triethylamine,
Tripropylamine, tributylamine, (e) Other solvents such as dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethylurea, anisole, water, benzene, toluene, o-xylene, m-xylene, p -Xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p
-Dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene,
m-bromotoluene, p-bromotoluene, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol,
Examples thereof include butanol, isobutanol, pentane, hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, ethyl formate and the like. These solvents may be used alone or in combination of two or more.

Among the above organic solvents capable of dissolving the positive photosensitive resin composition of the present invention, cyclopentanone, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N- Diethylacetamide and N-methyl-2-pyrrolidone are particularly preferable in terms of the smoothness of the obtained film and the storage stability of the resin composition.

The positive photosensitive resin composition of the present invention contains, in addition to the polyimide and the photosensitizer as its composition components, any other component such as a sensitizer, a photopolymerization initiator, a leveling agent, depending on the purpose. It may contain a coupling agent, a monomer, an oligomer, a stabilizer, a wetting agent, a pigment, a dye or the like.

The positive photosensitive resin composition of the present invention may be produced by any method, but the solvent 10
It is preferable to dissolve 1 to 100 parts by weight of polyimide, more preferably 5 to 70 parts by weight, and 0.01 to 200 parts by weight, more preferably 0.1 to 100 parts by weight of 0 parts by weight of polyimide. The positive photosensitive resin composition of the present invention can also be obtained by directly adding a photosensitizer to a polyimide solution obtained after producing a polyimide. In producing the positive photosensitive resin composition of the present invention, a step of filtering with a filtration membrane such as a Teflon (registered trademark) filter or degassing under reduced pressure may be added, if necessary. The method for producing a relief pattern of the present invention is characterized by comprising a step of coating the positive photosensitive resin composition on a supporting substrate and drying, an exposing step, a developing step and a heat treatment step.

When the positive type photosensitive resin composition of the present invention is applied, it is applied on a suitable support such as a silicon wafer, a copper substrate, an aluminum substrate or a glass substrate. In the case of a semiconductor manufacturing apparatus, the applied amount is such that the final film thickness after curing is 0.
It is applied so as to be 1 μm to 30 μm. Examples of the coating method include, but are not limited to, coating using a spin coater, coating using a spray coater, coating using a bar coater, dipping, and printing. After application, the film is dried by prebaking at 50 ° C to 250 ° C. In the exposure step, 150-500 nm ultraviolet ray and / or near-ultraviolet-visible ray is irradiated, but especially 365
A wavelength region centered on the wavelength of nm is desirable because a high effect can be obtained. A photomask pattern having a desired shape can be used in the exposure step. A relief pattern is obtained by dissolving and removing the irradiated portion with a developing solution. Examples of the developer include inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine; di-n.
-Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as monoethanolamine, dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like It is possible to use an aqueous solution of an alkali such as a quaternary ammonium salt, or an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant is added. The developing method is not particularly limited, but, for example, a known method such as dipping, spraying, ultrasonic wave, or paddle can be used. The relief pattern formed by development may be rinsed. The rinse liquid is not particularly limited, but for example,
Distilled water or ion-exchanged water can be used. Finally, heat treatment is performed to remove the solvent. Conventionally, high temperature treatment of about 200 to 300 ° C. is not required unlike the case of using polyamic acid, and low temperature heating of about 100 to 200 ° C. is sufficient. Through the above steps, a relief pattern having excellent heat resistance can be obtained.

[0058]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 [Synthesis of Polyimide] Nitrogen introduction tube, thermometer, reflux condenser,
And 5,7-diamino-1,1,4,6-tetramethylindane 1.360 in a 5-neck reactor equipped with a stirrer.
7 g (0.00666 mol), 3,5-diaminobenzoic acid 2.0297 g (0.01334 mol), 2,2
-Bis (3,4-dicarboxyphenyl) -1,1,
1,3,3,3-hexafluoropropane dianhydride 8.
7516 g (0.0197 mol), 0.0889 g (0.0006 mol) of phthalic anhydride as an end-capping agent, and 3.8 g of p-toluenesulfonic acid monohydrate as a catalyst.
02 mol) and pyridine 1.6 g (0.02 mol)
Was weighed. 50% N-methyl-2-pyrrolidone
g and 50 g of toluene were added, the mixture was stirred under a nitrogen atmosphere, heated to 150 ° C. over 2 hours, and then reacted at 150 ° C. for 10 hours. Water generated during the reaction was removed from the system by azeotropic distillation with toluene. After cooling to 30 ° C. and discharging the resulting viscous polymer solution into 2 liters of strongly stirred methanol, a white powdery precipitate was obtained, which was filtered off. This precipitate was further washed with 100 ml of methanol and filtered off. The white powder is reduced to 100
Dry at 48 ° C for 48 hours.

The logarithmic viscosity, glass transition temperature, and 5% weight loss temperature of the obtained polyimide powder are as follows. Logarithmic viscosity: 0.39 dl / g Glass transition temperature: Not observed 5% weight loss temperature: 464 ° C. [Preparation of positive photosensitive resin composition] Synthesized polyimide 1
00g, and 1,2- having the structure of the following formula (Formula 13)
30 g of the naphthoquinone-2-diazide-5-sulfonic acid ester compound was dissolved in 400 g of N-methyl-2-pyrrolidone and then filtered through a 0.5 μm Teflon filter to obtain a photosensitive resin composition.

[0061]

[Chemical 13]

[Characteristic Evaluation] The positive photosensitive resin composition was applied on a mirror-finished copper foil (thickness 30 μm) by using a spin coater, and then dried in an oven at 80 ° C. for 30 minutes to give a film thickness of about 5 μm. A coating film of The coating film was irradiated with 365 nm (i-line) at 300 mJ / cm ² through an L / S photomask. Next, the exposed portion was dissolved and removed by immersing it in a 10% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then rinsed with distilled water for 30 seconds. Subsequently, it was dried in an oven at 80 ° C. for 30 minutes. As a result, it was confirmed that a good L / S pattern was formed.
Residual film rate at this time (film thickness after development / film thickness before development × 10
0) was 94% and the resolution was 5 μm.

[Storage Stability] The above positive type photosensitive resin composition was shielded from light and allowed to stand at room temperature for 1 month, but no deterioration in quality such as decrease in molecular weight of polyimide, gelation, precipitation of foreign matter, cloudiness was observed. It was

[Solubility of positive photosensitive resin composition in solvent]
100 g of synthesized polyimide, and 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester compound 30
The solvent solubility of the positive photosensitive resin composition was evaluated by adding 400 g of solvent to g and stirring the mixture to confirm the presence or absence of insoluble matter. It was confirmed to be soluble in N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, cyclopentanone, cyclohexanone, and chloroform.

[0065]

The positive photosensitive resin composition according to the present invention has high heat resistance, solvent solubility, low dielectric constant, low stress, mechanical stability, low linear expansion coefficient, low hygroscopicity and adhesiveness. In addition, since it has extremely high sensitivity and high resolution photosensitivity, it can be used for electronics, paints, printing inks, printing plates, including interlayer insulating films and surface protective films for semiconductor devices, thin film devices, etc.
Widely useful in areas such as adhesives.

One of the effects of the present invention is to provide a positive type photosensitive resin composition containing a polyimide having photosensitivity capable of simultaneously exhibiting remarkably excellent high sensitivity and remarkably excellent high resolution. Is possible.

One of the effects of the present invention is a relief using a positive type photosensitive resin composition containing a polyimide having photosensitivity capable of simultaneously exhibiting remarkably excellent high sensitivity and remarkably excellent high resolution. It is possible to provide a method for manufacturing a pattern.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masashi Tamai             32 Mitsui Chemicals, 580 Nagaura, Sodegaura City, Chiba Prefecture             Corporation F-term (reference) 2H025 AA01 AA02 AA10 AA13 AA20                       AB16 AC01 AD03 BE01 CB25                       CB43 CB45 FA29                 4J043 PA04 PB08 PB14 PB15 QB26                       RA34 SA06 SA14 SA43 SA44                       SA47 SA54 SA61 SA62 SA71                       SB03 TA22 UA032 UA041                       UA081 UA091 UA121 UA122                       UA131 UA132 UA141 UA142                       UA151 UA152 UA161 UA171                       UA241 UA262 UA761 UA762                       UA771 UB011 UB021 UB022                       UB061 UB062 UB121 UB122                       UB131 UB132 UB141 UB151                       UB152 UB281 UB282 UB30                       UB301 UB351 UB401 UB402                       VA041 VA081 VA091 XA13                       XB13 XB14

Claims (6)

[Claims] 1. (a) General formula (I) (Chemical formula 1) (In the formula, n is a rational number in the range of 0 <n <100 and represents a copolymerization ratio in the resin. R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Represents a group, R ₃ represents a divalent organic group that imparts an alkali-soluble function to the resin, Z represents a tetravalent aromatic group, and (b) a polyimide having a repeating unit represented by A positive photosensitive resin composition comprising a photosensitizer. 2. The positive photosensitive resin composition according to claim 1, wherein R ₃ in the general formula (I) is a divalent organic group having at least one carboxyl group or hydroxyl group. 3. In the general formula (I), Z is represented by the following formula (Formula 2): (In the formula, W is a direct bond, -CH _2- , -O-, -SO _2- , -S
-, - CO -, - C (= N 2) -, it represents an isopropylidene group, a group selected from the group consisting of isopropylidene group that is hexafluorinated. Each r independently represents an alkyl group having 1 to 4 carbon atoms, a halogen group, a phenyl group or a hydrogen atom. a represents the integer of 1-3. 3. The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition is selected from the group consisting of: 4. The photosensitizer of (b) is a 1,2-naphthoquinonediazide-4-sulfonic acid ester compound and / or 1,
It is a 2-naphthoquinone diazide-5-sulfonic acid ester compound, The positive photosensitive resin composition in any one of Claim 1 thru | or 3 characterized by the above-mentioned. 5. The photosensitizer of (b) is 1,2-
The positive photosensitive resin composition according to claim 4, which is selected from a naphthoquinone diazide-4-sulfonic acid ester compound and / or a 1,2-naphthoquinone diazide-5-sulfonic acid ester compound. [Chemical 3] 6. A relief pattern comprising a step of coating the positive photosensitive resin composition according to claim 1 on a supporting substrate and drying, an exposing step, a developing step and a heat treating step. Production method.