JPH11209611A - Photosensitive polyimide precursor composition and production of pattern by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which has high sensitivity and therefore can form a good pattern even in a low exposure by incorporating a photosensitive polyimide precursor having photosensitive groups and acidic groups, a photosensitizer, and a non-photosensitive compound having groups soluble in an aqueous alkali solution. SOLUTION: There is provided a polyimide precursor composition containing 100 pts.wt. photosensitive polyimide precursor having repeating units represented by the formula and having photosensitive groups and acidic groups; 0.1-15 pts.wt. photosensitizer such as an aromatic bisimidazole compound; and 1-20 pts.wt. non-photosensitive compound having groups soluble in an aqueous alkali solution and having a boiling point of 150 deg.C or above such as 4,4'-dihydroxyphenyl sulfone, and 0.1-15 pts.wt. sensitizer comprising an aromatic mercapto compound such as 2-mercaptobenzothiazole. In the formula, R<1> is a tetravalent organic group; R<2> is a trivalent or tetravalent organic group; R<3> is a monovalent organic group having a photosensitive group; A is an acidic group; and n is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide precursor composition containing a polyimide precursor suitable as a material for a protective film such as a surface coat film of a semiconductor element and an interlayer insulating film of a thin-film multilayer wiring board. The present invention relates to a method for manufacturing a pattern.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive polyimide precursor composition, an olefinic aromatic tetracarboxylic acid obtained by reacting an aromatic tetracarboxylic dianhydride with an olefinically unsaturated alcohol described in Japanese Patent Publication No. 5-67026 is disclosed. Synthesis of acid diester, polymerization of this compound and diamine by a dehydration condensation reaction using carbodiimides, and a polyimide precursor containing a photosensitive group introduced by a covalent bond, described in JP-B-63-31939. Further, there is known a compound in which an amine compound having a photosensitive group is ion-bonded to a polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine to introduce a photosensitive group.

[0003] Each of these is applied to a substrate in the form of a varnish dissolved in an appropriate organic solvent, dried to form a film, and then irradiated with ultraviolet rays through an appropriate photomask to negatively cure the exposed portion. This is a type photosensitive composition, which is obtained by developing and rinsing with an organic solvent to obtain a relay pattern.

However, when an organic solvent is used as a developing solution at the time of pattern formation, swelling of the exposed portion tends to occur at the time of development, and it is difficult to obtain a high-resolution pattern.
In addition, when an organic solvent is used, there is also a problem that the health of workers is adversely affected, and waste liquid treatment is troublesome.

Therefore, as a material which can be developed with an aqueous solution, which solves the above-mentioned problems, for example, a positive type polymer in which a naphthoquinonediazidosulfonylamide group is introduced into a carboxyl group of a polyamic acid has been proposed (particularly). Japanese Patent Publication No. Hei 6-358835). This polymer is
Since the naphthoquinonediazidosulfonylamide group is changed to a carboxyl group by light irradiation, the exposed portion is characterized by being solubilized in an alkaline aqueous solution, and is known as a positive photosensitive polyimide precursor. However, at present, such a positive photosensitive polyimide precursor has not been obtained which has high sensitivity, excellent patternability, and performance for practical use.

On the other hand, as a negative type photosensitive polyimide precursor composition, at present, a high-resolution pattern which can be obtained and which can be developed with an alkaline aqueous solution has not been obtained.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to enable development in a short time with an aqueous solution, improve the working efficiency, and improve the photosensitive characteristics, especially the i-line photosensitive characteristics. An object of the present invention is to provide a photosensitive polyimide precursor composition which is excellent, has high sensitivity, can obtain a pattern having a good shape even at a low exposure dose, and can increase the residual film ratio after development. Another object of the present invention is to provide a photosensitive polyimide precursor composition having excellent cured film properties in addition to the above properties. It is still another object of the present invention to provide a pattern manufacturing method capable of shortening a manufacturing process and reducing a manufacturing cost in addition to the above characteristics.

[0008]

SUMMARY OF THE INVENTION The present invention provides a photosensitive polyimide comprising a photosensitive polyimide precursor having a photosensitive group and an acidic group, a photosensitive agent and a non-photosensitive compound having a group soluble in an aqueous alkali solution. The present invention relates to a polyimide precursor composition. In the present invention, the photosensitive polyimide precursor having a photosensitive group and an acidic group may be a compound represented by the general formula (I):

[0009]

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Wherein R ¹ is a tetravalent organic group, R ² is a trivalent or tetravalent organic group, two R ³ are each independently a monovalent organic group having a photosensitive group, and A is an acidic group. Wherein n is 1 or 2
Which has a repeating unit represented by:
The present invention relates to the photosensitive polyimide precursor composition. The present invention also provides a non-photosensitive compound having a soluble group in an alkaline aqueous solution, which has a boiling point of 150 ° C. or higher at normal pressure and has a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phenolic hydroxyl group or an alcoholic hydroxyl group. 3. The photosensitive polyimide precursor composition according to claim 1, wherein

The present invention also provides a method for irradiating a film formed using the photosensitive polyimide precursor composition with light through a photomask having a predetermined pattern, and then developing the film using an alkaline aqueous solution. And a method for producing a pattern.

Further, the present invention relates to the above-mentioned method for producing a pattern, wherein the irradiation light is i-line.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The polyimide precursor used in the photosensitive polyimide precursor composition of the present invention has a photosensitive group and an acidic group. Is necessary to obtain a polyimide precursor having

The polyimide precursor is generally a polyamic acid having a structural unit consisting of a tetracarboxylic acid residue and a diamine residue or a derivative thereof, and the photosensitive group may be bonded to the tetracarboxylic acid residue. And may be bonded to a diamine residue. Similarly, an acidic group may be bonded to a tetracarboxylic acid residue or a diamine residue.

An example of a polyimide precursor in which a photosensitive group is bonded to a tetracarboxylic acid residue and an acidic group is bonded to a diamine residue is a polyimide precursor which is not involved in the formation of an amide bond by reaction with a diamine. A polyimide precursor in which a photosensitive group is introduced by utilizing a carboxyl group through an ester bond, an amide bond, or the like, and in which an acidic group is bonded as a side chain of the diamine, may be mentioned. On the other hand, an example of a polyimide precursor in which an acidic group is bonded to a tetracarboxylic acid residue and a photosensitive group is bonded to a diamine residue is one that does not participate in the formation of an amide bond by reaction with a diamine. Alternatively, a polyimide precursor in which two carboxyl groups remain as they are and a photosensitive group is introduced into a side chain of a diamine residue through an ester bond, an amide bond, an ether bond, an amino bond, or the like. As a method of introducing a photosensitive group into a side chain of a diamine residue, a diamine having a functional group such as a hydroxyl group, a carboxyl group, or an amino group is reacted with a compound having a group reactive with a pre-functional group and a compound having a photosensitive group. And the like.

Among these, the photosensitive polyimide precursor used in the present invention exhibits good photosensitive properties and developability in an aqueous alkali solution, and a photosensitive group is bonded to a tetracarboxylic acid residue and a diamine residue is present. A polyimide precursor in which an acidic group is bonded to the group is preferable, and a polyimide precursor having a repeating unit represented by the above general formula (I) is more preferable because of easy production.

In the repeating unit represented by the general formula (I), the tetravalent organic group represented by R ¹ is a residue of a tetracarboxylic acid capable of reacting with a diamine to form a polyimide resin, or a derivative thereof. It is preferable that it is a tetravalent organic group having 4 or more carbon atoms from the viewpoints of mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by curing. Preferred examples thereof are shown in the following structural formula group. Among the tetravalent organic groups having 4 or more carbon atoms, organic groups having a total carbon number of 6 to 30 including an aromatic ring (benzene ring, naphthalene ring, etc.) are more preferable. In the polyimide precursor molecule, in the repeating unit that is present in a plurality,
All R ¹ may be the same or different.

[0018]

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[0019]

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[0020]

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In the photosensitive polyimide precursor, acidic
A group represented by, that is, represented by A in the general formula (I)
The sulfonic acid group (-) is not particularly limited.
SO _ThreeH), sulfinic acid group (-SO_TwoH), Carboki
No sil group (-COOH) or phenolic hydroxyl group
It is preferable to use this as it exhibits good solubility. This
Among them, carboxyl groups and hydroxyl groups are polyimides.
It is particularly preferable because the synthesis of the precursor is easy.

In the general formula (I), R ² to which the acidic group A is bonded is preferably a diamine residue capable of forming a polyimide resin by reacting with a tetracarboxylic acid or a derivative thereof. From the viewpoint of mechanical properties, heat resistance and adhesiveness of the obtained polyimide film, it is preferably a trivalent or tetravalent organic group containing an aromatic ring, and the mechanical properties, heat resistance and From the viewpoint of adhesion, a trivalent or tetravalent organic group containing an aromatic ring and having 6 to 30 carbon atoms in total is more preferable. Specific preferred examples are shown in the following structural formula groups. Note that all R ² in the molecule may be the same or different.

[0023]

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(Where Z is

[0025]

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In the photosensitive polyimide precursor, a group containing a photosensitive group,
In the repeating unit represented by the general formula (I), the group represented by R ³ is, for example, a group which is eliminated by light irradiation, a group which can be dimerized or copolymerized by light irradiation, and the like.
Among them, a group having a polymerizable unsaturated double bond is preferable because good photosensitivity can be easily imparted. As the group having a polymerizable unsaturated double bond, for example, the following general formula

[0027]

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(Where R ⁴ , R ⁵ and R ⁶ are each independently selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, and R ⁷ represents a divalent organic group) The organic group represented by the formula (1) is preferable because it can impart high-sensitivity photosensitivity. The alkyl group preferably has 1 to 4 carbon atoms. The divalent organic group represented by R ⁷ is preferably an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, and a propylene group.
In particular, a methacryloyloxyalkyl group and an acryloyloxyalkyl group (having an alkyl group having 1 to 20 carbon atoms) are suitable for the present invention because they not only realize high sensitivity but also are easy to synthesize. The polyimide precursor used in the present invention may include a repeating unit represented by the general formula (II) together with the repeating unit represented by the general formula (I).

[0029]

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(Wherein R ⁸ is a tetravalent organic group, R ⁹ is a divalent organic group, R ¹⁰ is a monovalent organic group or a hydroxyl group, and contains a repeating unit represented by the general formula (I). Is a repeating unit expressed as Specific examples of the tetravalent organic group represented by R ⁸ include the same as the organic group represented by R ¹ , and preferred examples thereof are also the same. Specific examples of the monovalent organic group represented by R ¹⁰ Examples thereof include a group in which the organic group represented by R ³ is bonded via an oxygen atom. Preferred examples are also the same, but in addition, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an alkoxy group such as n-butoxy group; an aryloxy group such as benzyloxy group; an alkylamino group; a dialkylamino group;
Anilino group; may include a toluidino group and the like. In the case of these other groups, those having 1 to 20 carbon atoms in total are preferred.

R⁹Is a divalent organic group.
Of mechanical properties, heat resistance, adhesiveness, etc. of polyimide film
And those containing an aromatic ring or silicon are preferred. Aromatic ring
(Poly) siloxa having 1 to 10 carbon atoms
Those having an union bond are preferred. Represented by the general formula (II)
When more than one structural unit is present in the molecule, ⁹
May be the same or different. R⁹The following are preferred examples of
Shown in

[0032]

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[0033]

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When the repeating units represented by the general formulas (I) and (II) are used as the polyimide precursor of the present invention, the ratio of (I) is represented by the molar percentage of each repeating unit. 10 to 100 mol%, (I
It is preferred that I) is 90 to 0 mol% because of excellent balance between developability in an alkaline aqueous solution and a good pattern shape.
It is preferred that I) is from 20 to 0 mol%. Further, it is preferable that 10 to 100 mol% of the photosensitive group be the photosensitive group in the polyimide precursor side chain, that is, the total of the groups represented by R ³ and R ¹⁰ . When having a group other than a photosensitive group,
From the viewpoint of film properties, an alkyl group having 4 or less carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group are particularly preferable.

The molecular weight of the polyimide precursor in the present invention is preferably 10,000 to 200,000, more preferably 15,000 to 50,000 in terms of weight average molecular weight from the viewpoint of the properties of the cured film after imidization. The weight average molecular weight can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. The polyimide precursor used in the present invention is prepared by mixing and reacting a tetracarboxylic dianhydride and a hydroxy group-containing compound to produce a half ester of tetracarboxylic acid, and then acid chloride with thionyl chloride, followed by reaction with a diamine. And a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent.

The tetracarboxylic dianhydride includes:
For example, oxydiphthalic acid, pyromellitic acid, 3,
3 ′, 4,4′-benzophenonetetracarboxylic acid,
3,3 ′, 4,4′-biphenyltetracarboxylic acid,
1,2,5,6-naphthalenetetracarboxylic acid, 2,
3,6,7-naphthalenetetracarboxylic acid, 1,4
5,8-naphthalenetetracarboxylic acid, 2,3,5,6
-Pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, sulfonyldiphthalic acid, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic acid,
p-terphenyl-3,3 ', 4,4'-tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,
2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis {4 ′-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, 1,1, 1,3,3,3-hexafluoro-2,2
-Bis {4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl} propane, having the following general formula (III)

[0037]

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(Wherein, R ¹¹ and R ¹² represent a monovalent hydrocarbon group, which may be the same or different, and s is 1
And dihydrates of tetracarboxylic acids such as aromatic tetracarboxylic acids such as tetracarboxylic acids represented by the following formulas. These are used alone or in combination of two or more. Among them, a tetracarboxylic acid giving the structure shown as a preferable example of R ¹ in the general formula (I) is preferable.

The diamine which gives the diamine residue R ² in the repeating unit represented by the general formula (I) includes 3,
5-diaminobenzoic acid, 4,4'-dihydroxy-3,
3′-diaminobiphenyl, 3,4-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,3-diamino-4-hydroxypyridine,
2,2-bis (4-hydroxy-3-aminophenyl)
Hexafluoropropane, 2,4-diaminophenol, 2,4-diaminobenzoic acid, 3-carboxy-
4,4'-diaminodiphenyl ether, 3,3'-dicarboxy-4,4'-diaminophenyl ether,
-Carboxy-4,4'-diaminophenylmethane,
3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,3′-dicarboxy-4,4′-3,
3 ', 5,5'-tetracarboxy-4,4'-3,
3'-dicarboxy-4,4'-diaminodiphenylmethane, 3-carboxy-4,4'-diaminodiphenylsulfone, 1,1,1,3,3,3-hexafluoro-
2,2-bis (3-carboxy-4-aminophenyl)
And propane.

The diamine providing the diamine residue R ⁹ in the repeating unit represented by the general formula (II) includes:
4,4'- (or 3,4'-3,3'-2,4'-2,
2 ′-) diaminodiphenyl ether, 4,4 ′-(or 3,4′-3,3′-2,4′-2,2 ′-) diaminodiphenylmethane, 4,4 ′-(or 3,4′-) 3,
3'-2,4'-2,2 '-) diaminodiphenylsulfone, 4,4'-(or 3,4'-3,3'-2,4 '
-2,2 '-) diaminodiphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylenediamine, m-xylenediamine, o-tolidine,
o-tolidine sulfoaniline, 4,4′-methylene-bis- (2,6-diethylaniline), 4,4′-methylene-bis- (2,6-diisopropylaniline), 2,
4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4′-benzophenonediamine, bis- {4-
(4′-aminophenoxy) phenyl} sulfone, 1,
1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 2,2-bis {4-
(4'-aminophenoxy) phenyl @ propane, 3,
3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl4,4′-diaminodiphenylmethane, bis {4- (3′-aminophenoxy) phenyl} sulfone, 2, 2-bis (4-aminophenyl) propane and the like are used, and these are used alone or in combination of two or more. In addition, as a diamine which gives a diamine residue R ⁹ in the repeating unit represented by the general formula (II), the following general formula (IV)

[0041]

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(Where R¹³And R¹⁴Is a divalent hydrocarbon group
And each may be the same or different, and R^FifteenPassing
And R¹⁶Represents a monovalent hydrocarbon group.
And t is an integer of 1 or more).
Use diamines such as diaminopolysiloxane
Can also. R¹³And R¹⁴As a methylene group, ethyl
Alkylene group such as phenyl group, propylene group, etc., phenylene group
And the like, and their bonding groups.
^FifteenAnd R ¹⁶Are methylene, ethylene, propylene
Arylene such as alkylene group and phenylene group
Group. When these are used, all amine components
Is preferably used in an amount of 1 to 30 mol%. Ma
Further, di in the repeating unit represented by the general formula (II)
Amine residue R⁹As a diamine to improve heat resistance
And 4,4'-diaminodiphenyl ether-3-
Sulfonamide, 3,4'-diaminodiphenylate
Ru-4-sulfonamide, 3,4'-diaminodiphenyl
Ruthel-3'-sulfonamide, 3,3'-diami
Nodiphenyl ether-4-sulfonamide, 4,4 '
-Diaminodiphenyl ether-3-carboxamide,
3,4'-diaminodiphenyl ether-4-carboxy
Samide, 3,3'-diaminodiphenyl ether-4-
Sulfonamide group such as carboxamide or carboxamido
It is also possible to use a diamine compound having a silyl group.
When these are used, 1 to 30 with respect to all amine components
It is preferable to use mol%. These general formulas (II)
The diamine residue R in the repeating unit represented by⁹Give
Diamines can be used alone or in combination of two or more.
Used.

The photosensitive polyimide precursor composition of the present invention contains a sulfonic acid group, a sulfinic acid group, a carboxyl group, and a phenolic hydroxyl group in order to improve developability, shorten development time, and further improve patternability. And a non-photosensitive compound having a group soluble in an aqueous alkali solution such as an alcoholic hydroxyl group. Among these, compounds having a carboxyl group or a phenolic hydroxyl group,
It is particularly preferable because it has excellent developability and patternability. These compounds preferably have a boiling point of 150 ° C. or higher at normal pressure. If it is less than this value, it tends to volatilize during baking during pattern formation, failing to obtain a sufficient effect and affecting the photosensitive characteristics. Specific examples of such a compound include benzoic acid, p (or o, m) -methylbenzoic acid, 2,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, p (or m) -dimethylaminobenzoic acid Acid, terephthalic acid, aromatic carboxylic acid such as isophthalic acid, 4,4′-dihydroxybiphenyl,
3,3′-dihydroxybiphenyl, 3,3′-dicarboxy-diphenylmethane, 3,3′-dicarboxybiphenyl, 3,3′-dicarboxydiphenylsulfone, p (or o, m) -cresol, phloroglucin,
Pyrogallol, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenylsulfone, tris (4-hydroxyphenyl) methane, 2-methyl-1
Aromatic compounds having a phenolic hydroxyl group such as -naphthol, 2-hydroxy-2-phenylpropane, 1,3-bis (1-hydroxy-1-methylethyl) benzene, and 1,4-benzenedimethanol are preferred. Is raised. It is also possible to use a high molecular weight compound having the above substituents as the compound, for example, a novolak resin obtained by condensing phenols and aldehydes, a homopolymer or copolymer of hydroxystyrene, and acrylic acid as a monomer. And a polyamic acid obtained by condensation of an acid dianhydride and a diamine. The monomers used for these polymers and the molecular weight of the resulting polymer may be in any range as long as the solubility in an aqueous alkaline solution is not impaired, and is not particularly limited. Among the above compounds, the use of a polyamic acid containing a repeating unit represented by the general formula (V) is particularly preferable from the viewpoint of the adhesiveness of the composition, the film shrinkage after curing, and the like.

[0044]

Embedded image (In the formula, R ¹⁷ is a tetravalent organic group, and R ¹⁸ is a divalent organic group. Specific examples of the tetravalent organic group represented by R ¹⁷ are the same as the organic group represented by R ^8. R ¹⁸ is a divalent organic group, specific examples of which are the same as the organic groups represented by R ⁹ , and preferable examples are also the same. The molecular weight of this polyacid acid is preferably 10,000 to 50,000 in terms of weight average molecular weight, and these may be used alone or in combination of two or more.The content in the composition is 100 parts by weight of the polyimide precursor , Preferably 1 to 20 parts by weight,
The content is more preferably 1 to 15% by weight, further preferably 1 to 10% by weight. Outside the range of 1 to 20 parts by weight, the patternability and the properties of the cured film tend to be adversely affected.

The photosensitive polyimide precursor composition of the present invention contains a photosensitizer (photoinitiator, photoinitiator).
Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone, 4,4′-bis (pN, N-diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, , 2-Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl,
Diphenyl disulfide, phenanthrenequinone, 2-
Isopropylthioxanthone, riboflavin tetrabutyrate, N-phenyldiethanolamine, 2- (o-
Ethoxycarbonyl) oxyimino-1,3-diphenylpropanedione, 1-phenyl-2- (o-ethoxycarbonyl) oxyiminopropan-1-one, 3,
3,4 ′, 4′-tetra (t-butylperoxycarbonyl) benzophenone, N- (p-cyanophenyl) glycine, N- (p-methylsulfonylphenyl) glycine, 2,2 ′, 4,4 ′, 5,5'-hexaphenylbisimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (o-fluorophenyl)-
4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′-bis (o-trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′- Bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (p-methoxyphenyl) bisimidazole, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetra- (m-methoxyphenyl) bisimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra- (3,4 -Dimethoxyphenyl) bisimidazole, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2
(1H-pyrrol-1-yl) propyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-
Difluoro-3- (2 (1H-pyrrol-1-yl) methyl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyrrole-1)
-Yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-dimethylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3
-(2,5-diethylpyrrol-1-yl) phenyl]
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3- (2,5-diisopropylpyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2,5-
Bis (dimethylaminopyrrole-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-
Difluoro-3- (2,5-dimethyl-3-methoxypyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methoxyphenyl] titanium, bis (cyclo Pentadienyl)
-Bis [2,6-difluoro-3-isopropoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-n-propoxyphenyl]
Examples include, but are not limited to, titanium and the like. In particular, aromatic bisimidazole compounds and titanocene compounds are preferable, and these are used alone or in combination of two or more. The content in the composition is not particularly limited, but may be 0.1 to 100 parts by weight of the polyimide precursor.
It is preferable that the content be 1 to 15.0 parts by weight,
It is more preferred to be 8.0 parts by weight.

In the present invention, it is preferable to use an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure. When the boiling point is lower than 100 ° C. at normal pressure, when the solvent contained in the system is removed by drying or the like or when irradiating with an actinic ray, the addition-polymerized compound tends to volatilize and deteriorate the properties. The addition polymerizable compound is preferably soluble in an organic solvent. Examples of the addition-polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure include compounds obtained by condensing a polyhydric alcohol with an α, β-unsaturated carboxylic acid [eg, ethylene glycol di (meth) acrylate (diacrylate) Or the meaning of dimethacrylate, hereinafter the same), triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,2- Propylene glycol di (meth) acrylate, di (1,2-propylene glycol) di (meth) acrylate, tri (1,2-propylene glycol) di (meth) acrylate, tetra (1,2-propylene glycol) di (meth) ) Acrylate, dimethyla Minoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, etc.]. Other, styrene,
Divinylbenzene, 4-vinyltoluene, 4-vinylpyrudine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethyl Acrylamide, N-methylol acrylamide, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolpropanetetra (meth)
Acrylate and the like. These are used alone or in combination of two or more.

Examples of the organic solvent used in the photosensitive polyimide precursor composition of the present invention include acetone, methyl ethyl ketone, diethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-
Propanol, 1-butanol, 2-butanol, t-
Butanol, ethylene glycol monomethyl ether,
Xylene, tetrahydrofuran, dioxane, cyclopentanone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ
-Butyrolactone, dimethylsulfoxide, ethylene carbonate, propylene carbonate, urholane, hexamethylenephosphortriamide, N-acetyl-ε-
Preferred examples include caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. These may be used alone or as a mixed system. The content in the composition is not particularly limited,
100 to 300 parts by weight of the polyimide precursor, 10 to 300
It is preferable to set it as a weight part, and it is more preferable that it is 150-200 weight part. The photosensitive polyimide precursor composition of the present invention may contain a sensitizer as needed. Examples of the sensitizer include 7-N, N-diethylaminocoumarin, 7-diethylamino-3-thenonylcoumarin,
3,3′-carbonylbis (7-N, N-diethylamino) coumarin, 3,3′-carbonylbis (7-N, N
-Dimethoxy) coumarin, 3-thienylcarbonyl-7
-N, N-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-N, N-methoxycoumarin, 3- (4'-methoxybenzoyl) coumarin, 3,
3'-carbonylbis-5,7- (dimethoxy) coumarin, benzalacetophenone, 4'-N, N-dimethylaminobenzalacetophenone, 4'-acetoaminobenzal-4-methoxyacetophenone and the like.
The use amount of these sensitizers is not particularly limited, but when used, it is preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the polyimide precursor,
The range is more preferably from 0.3 to 20 parts by weight.

The photosensitive polyimide precursor composition of the present invention may optionally contain an aromatic mercapto compound. Examples of such an aromatic mercapto compound include those having one or two mercapto groups having benzene or a heterocyclic ring as a mother nucleus. In the case of disubstitution, one of the mercapto groups is an alkyl group. , Aralkyl or phenyl-substituted, and further, a dimer in the form of an alkylene group-interposed dimer or disulfide. Among these aromatic mercapto compounds, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and the like are preferred. These are used alone or in combination of two or more. The content of the composition is the polyimide precursor 100
The amount is preferably 0.1 to 15.0 parts by weight, more preferably 0.1 to 5.0 parts by weight, based on parts by weight. The photosensitive polyimide precursor composition of the present invention may contain other additives, for example, additives such as a plasticizer and an adhesion promoter.

In the method for producing a pattern according to the present invention, a polyimide film comprising a cured product of the photosensitive polyimide precursor composition of the present invention is formed by photolithography using the composition. In the pattern manufacturing method of the present invention, first, a film made of the photosensitive polyimide precursor composition of the present invention is formed on a support substrate surface. In the pattern manufacturing method of the present invention, the surface of the support substrate may be treated in advance with an adhesion aid in order to improve the adhesion between the film or the polyimide film after heat curing and the support substrate.

The coating made of the photosensitive polyimide precursor composition is formed, for example, by forming a varnish film of the photosensitive polyimide precursor composition and then drying it. The varnish film is formed by a method appropriately selected from means such as spin coating using a spinner, dipping, spray printing, and screen printing, depending on the viscosity of the varnish. The thickness of the film can be adjusted by the application conditions, the solid content concentration of the present composition, and the like. In addition, the film formed on the support is peeled off from the support to form a sheet made of the polyimide precursor composition, and the sheet is attached to the surface of the support substrate to form the film described above. May be.

Next, after irradiating this film with light (usually using ultraviolet light) through a photomask of a predetermined pattern, the unexposed portion is dissolved and removed with a basic aqueous solution.
Obtain a desired relief pattern. This developing step may be performed using a normal photoresist developing device.

In the pattern manufacturing method of the present invention, an alkaline aqueous solution is used as a developer. The developer may be an aqueous solution of one compound or an aqueous solution of two or more compounds as long as it is an aqueous solution exhibiting alkalinity. The alkaline aqueous solution is usually a solution in which a basic compound is dissolved in water. The concentration of the basic compound is usually 0.1 to 50% by weight / weight%.
It is preferably 0.1 to 30% by weight / weight. In addition, a developer is used to improve the solubility of the polyimide precursor, such as methanol, ethanol, propanol, isopropyl alcohol, N-methyl-2-pyrrolidone, N, N
-It may further contain a water-soluble organic solvent such as dimethylacetamide.

Examples of the basic compound include hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium ions, amine compounds and the like. Specifically, 2-dimethylaminoethanol, 3
-Dimethylamino-1-propanol, 4-dimethylamino-1-butanol, 5-dimethylamino-1-pentanol, 6-dimethylamino-1-hexanol,
-Dimethylamino-2-methyl-1-propanol, 3
-Dimethylamino-2,2-dimethyl-1-propanol, 2-diethylaminoethanol, 3-diethylamino-1-propanol, 2-diisopropylaminoethanol, 2-di-n-butylaminoethanol, N, N
-Dibenzyl-2-aminoethanol, 2- (2-dimethylaminoethoxy) ethanol, 2- (2-diethylaminoethoxy) ethanol, 1-dimethylamino-2
-Propanol, 1-diethylamino-2-propanol, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N
-T-butyldiethanolamine, N-lauryldiethanolamine, 3-diethylamino-1,2-propanediol, triethanolamine, triisopropanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N
-N-butylethanolamine, Nt-butylethanolamine, diethanolamine, diisopropanolamine, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 6-amino-
1-hexanol, 1-amino-2-propanol, 2
-Amino-2,2-dimethyl-1-propanol, 1-
Aminobutanol, 2-amino-1-butanol, N-
(2-aminoethyl) ethanolamine, 2-amino-
2-methyl-1,3-propanediol, 2-amino-
2-ethyl-1,3-propanediol, 3-amino-
1,2-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, hydrogencarbonate Potassium, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, aminoethanol, 2-aminoethanol,
-Aminopropanol, 2-aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine,
It is preferable to use triethylamine, tripropylamine, triisopropylamine, or the like, but other compounds may be used as long as they are soluble in water and the aqueous solution exhibits alkalinity.

The relief pattern formed by development is then washed with a rinsing liquid to remove the developing solvent. Preferable examples of the rinsing liquid include methanol, ethanol, isopropyl alcohol, and water having good miscibility with the developing liquid.

The relief pattern obtained by the above treatment is obtained by partially imidizing the polyimide precursor of the present invention. This relief pattern is changed from 150 ° C. to 4
By performing the heat treatment at a temperature selected from the range up to 50 ° C., a pattern made of polyimide can be obtained with high resolution. This pattern has high heat resistance and excellent mechanical properties.

[0056]

The present invention will be described below with reference to examples. Examples 1 to 5 and Comparative Examples 1 and 2 (1) Synthesis of Polymer Synthesis Example 1 Synthesis of Synthetic Acid Chloride of Polyimide Precursor 3,3 ′, 4,4′-
Biphenyltetracarboxylic dianhydride (BPDA) 9.
42 g (0.032 mol), 8.32 g (0.064 mol) of 2-hydroxyethyl methacrylate (HEMA), 5.06 g (0.064 mol) of pyridine, 0.03 g of t-butylcatechol, N-methyl-2 When 70 ml of pyrrolidone (NMP) was added and stirred at 60 ° C., a clear solution was obtained in 2 hours. After stirring the solution at room temperature for 7 hours, the flask was cooled with ice and 9.88 g (0.083 mol) of thionyl chloride was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

Polyimide precursor (polyamic acid ester
In another 200 ml four-necked flask, 2.89 g (0.019 mol) of 3,5-diaminobenzoic acid and 2.54 g of 2,2′-dimethyl-4,4′-diaminobiphenyl
(0.012 mol), 5.06 g (0.064 g) of pyridine
Mol), 0.03 g of t-butylcatechol and 50 ml of N-methyl-2-pyrrolidone (NMP). Cool the flask with ice and stir (keeping the temperature at 10 ° C. or lower). Dropped slowly over time.
Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice with water, and dried under vacuum to obtain 22 g of a polyamic acid ester. The weight average molecular weight of this polyamic acid ester is determined by GP
When measured by C (gel permeation chromatography), it was 44000 in terms of polystyrene.

Synthesis Example 2 Synthesis of Synthetic Acid Chloride of Polyimide Precursor In a 200 ml four-necked flask, 9.92 g (0.032 mol) of 4,4′-oxydiphthalic dianhydride (ODPA), 2-hydroxyethyl Methacrylate (HEM
A) 8.32 g (0.064 mol), pyridine 5.06
g (0.064 mol), t-butylcatechol 0.03
g and 70 ml of N-methyl-2-pyrrolidone (NMP) were added and stirred at 60 ° C., and a clear solution was obtained in 2 hours. After the solution was stirred at room temperature for the next 7 hours, the flask was cooled with ice and 9.88 g of thionyl chloride (0.083
Mol) was added dropwise in 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

Polyimide precursor (polyamic acid ester
In another 200 ml four-necked flask, 4.10 g of 4,4'-dihydroxy-3,3'-diaminobiphenyl was added.
(0.019 mol), 2,2'-dimethyl-4,4'-
2.54 g (0.012 mol) of diaminodiphenyl, 5.06 g (0.064 mol) of pyridine, 0.03 g of t-butylcatechol, N-methyl-2-pyrrolidone (NM
P) The acid chloride solution obtained above was slowly added dropwise over 1 hour while cooling and stirring (keeping the temperature below 10 ° C.) the ice-cooled flask with 50 ml. Thereafter, the mixture was stirred at room temperature for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice with water, and dried under vacuum to obtain 22 g of a polyamic acid ester. The weight average molecular weight of this polyamic acid ester measured by GPC was 35,000 in terms of polystyrene.

Synthesis Example 3 Synthesis of Synthetic Acid Chloride of Polyimide Precursor 3,3 ′, 4,4′-
Biphenyltetracarboxylic dianhydride (BPDA) 9.
42 g (0.032 mol), 8.32 g (0.064 mol) of 2-hydroxyethyl methacrylate (HEMA), 5.06 g (0.064 mol) of pyridine, 0.03 g of t-butylcatechol, N-methyl-2 When 70 ml of pyrrolidone (NMP) was added and stirred at 60 ° C., a clear solution was obtained in 2 hours. After stirring the solution at room temperature for 7 hours, the flask was cooled with ice and 9.88 g (0.083 mol) of thionyl chloride was added dropwise over 10 minutes. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a solution containing acid chloride.

Polyimide precursor (polyamic acid ester
In a separate 200 ml four-necked flask, 2.43 g (0.016 mol) of 3,5-diaminobenzoic acid, 1.92 g (0.015 mol) of 4,4′-diaminobiphenyl ether, pyridine 5.06 g (0.064 mol), 0.03 g of t-butylcatechol, and 50 ml of N-methyl-2-pyrrolidone (NMP) were placed in the flask, and the flask was cooled with ice and stirred (keeping the temperature at 10 ° C or lower). The obtained acid chloride solution was slowly added dropwise over 1 hour. Then at room temperature
The mixture was stirred for 1 hour, poured into 1 liter of water, and the precipitated polymer was collected by filtration, washed twice with water, and dried under vacuum to obtain 22 g of a polyamic acid ester. The weight average molecular weight of this polyamic acid ester measured by GPC was 31,000 in terms of polystyrene.

(2) Preparation of polyimide precursor composition 10 g of the obtained polymer was mixed with 16 g of γ-butyrolactone,
Dissolved in 2 g of cyclopentanone, 2.5 g of tetraethylene glycol diacrylate, 5.0 g of 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 7-diethylamino -3-
After mixing 0.1 g of tenonyl coumarin and the alkali-soluble compound shown in Table 1, the mixture was filtered under pressure using a filter having a pore size of 3 μm to obtain a photosensitive polyimide precursor composition in the form of a solution.

(3) Formation of Pattern The photosensitive polyimide precursor composition prepared in (2) is spin-coated on a silicon wafer, and is coated on a hot plate.
Heating at 200 ° C. for 200 seconds gave a 15 μm thick coating. After exposing this coating film with an i-line stepper (300 mJ / cm ² ), it was immersed and developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Further rinse with water. At this time, the time required for all the unexposed portions of the film to dissolve was measured and defined as a development time. Also, the pattern shape after development was measured and observed, and the resolution and pattern shape were shown in Table 1.
It was shown to.

[0064]

[Table 1]

Examples 6 to 10 Using the patterns obtained in Examples 1 to 5, under a nitrogen atmosphere at 100 ° C. for 30 minutes, at 200 ° C. for 30 minutes, 35
Heating was performed at 0 ° C. for 60 minutes to obtain a polyimide pattern. The thickness of the obtained polyimide pattern was 10 μm, and a good polyimide pattern was obtained.

From Table 1, it can be seen that the photosensitive material of the present invention has a shorter development time and is more excellent in photosensitive characteristics and developability than the composition of the comparative example.

[0067]

The photosensitive polyimide precursor composition of the present invention (claim 1) can be developed with an aqueous solution in a short time, so that the working efficiency can be improved and the photosensitive characteristics, particularly, It is excellent in i-line photosensitive characteristics, has high sensitivity, can obtain a pattern having a good shape even at a low exposure dose, and can increase the residual film ratio after development. Further, the photosensitive polyimide precursor composition according to claim 2 has further excellent cured film properties in addition to the above effects. Further, the photosensitive polyimide precursor composition of claim 3 is particularly excellent in developability. According to the pattern manufacturing method of the fourth and fifth aspects, since the development can be performed in a short time with an aqueous solution, the working efficiency can be improved, and the photosensitive characteristics, particularly, the photosensitive characteristics at i-line are excellent. , High sensitivity, good shape pattern can be obtained even at low exposure,
A cured film having a high residual film ratio after development and having excellent cured film characteristics can be obtained, and further, the production process can be shortened and the production cost can be reduced.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Kiyotaka Mashimo 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref.

Claims (5)

[Claims] 1. A photosensitive polyimide precursor composition comprising a photosensitive polyimide precursor having a photosensitive group and an acidic group, a photosensitive agent and a non-photosensitive compound having an aqueous alkali solution-soluble group. 2. A photosensitive polyimide precursor having a photosensitive group and an acidic group is represented by the general formula (I): (Wherein, R ¹ is a tetravalent organic group, R ² is a trivalent or tetravalent organic group, two R ³ are each independently a monovalent organic group having a photosensitive group, and A is an acidic group. And n represents 1 or 2.) The photosensitive polyimide precursor composition according to claim 1, wherein the repeating unit is represented by the following formula: 3. A non-photosensitive compound having an alkali aqueous solution-soluble group having a boiling point of 150 ° C. or higher at normal pressure and having a sulfonic acid group, a sulfinic acid group, a carboxyl group, a phenolic hydroxyl group or an alcoholic hydroxyl group. The photosensitive polyimide precursor composition according to claim 1, wherein 4. After irradiating a film formed using the photosensitive polyimide precursor composition according to claim 1 with light through a photomask having a predetermined pattern, the film is treated with an alkali. A pattern manufacturing method characterized by developing with an aqueous solution. 5. The pattern manufacturing method according to claim 3, wherein the irradiation light is i-line.