JPH11209614A - 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, can form a good pattern even in a low exposure and can give a cured film having excellent properties by mixing a photosensitive polyimide precursor having photosensitive groups and acidic groups with a photosensitizer so as to form a composition which, when applied and dried, can give a film having a specified dissolution rate in a basic aqueous solution. SOLUTION: There is provided a polyimide precursor composition comprising 100 pts.wt. two photosensitive polyimide precursors having their respective repeating units represented by formulas I and II; 0.1-15 pts.wt. photoinitiator such as an aromatic imidazole compound; and 0.1-15 pts.wt. sensitizer or photoinitiation aid such as an aromatic mercapto compound or a coumarin compound, wherein a film obtained by applying and drying this composition has a dissolution rate of 0.01-0.5 μm/sec in a 2.38 wt.% aqueous tetramethylammonium hydroxide solution. In the formulae, R<1> and R<8> are each a tetravalent organic group; R<2> is a tri- or tetra-valent organic group; R<3> is an organic group having a photosensitive group; R<9> is a divalent organic group; R<10> is a monovalent organic group or hydroxyl; 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 or an interlayer insulating film of a thin film multilayer wiring board. The present invention relates to a method for manufacturing a pattern using an object.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive polyimide precursor composition, (i) an aromatic tetracarboxylic dianhydride described in JP-B-5-67026 is reacted with an olefinically unsaturated alcohol. An olefin aromatic tetracarboxylic acid diester is synthesized, this compound and a diamine are polymerized by a dehydration condensation reaction using carbodiimides, and a polyimide precursor containing a photosensitive group introduced through a covalent bond, (ii) Tokiko Sho 63 JP-A-31939 describes a polyamic acid obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine to which an amine compound having a photosensitive group is ion-bonded to introduce a photosensitive group. Are known.

[0003] All of these are 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 light-cur the exposed portion. A negative-type photosensitive composition, which is developed and rinsed with an organic solvent to form a relief /
That's what gets the pattern.

However, during development using an organic solvent as a developer during pattern formation, swelling of the exposed portion is apt to occur, 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 liquid, which solves the above problems, for example, a positive polymer in which a naphthoquinonediazidosulfonylamide group is introduced into a carboxyl group of polyamic acid has been proposed ( JP-A-6-258835). This polymer has a feature that the exposed portion is solubilized in a basic aqueous solution because a naphthoquinonediazidosulfonylamide group is changed to a carboxyl group by light irradiation, and is known as a positive photosensitive polyimide precursor.

However, at present, such a positive photosensitive polyimide precursor having high sensitivity, excellent pattern shape, and performance for practical use has not been obtained. On the other hand, as the negative type photosensitive group polyimide precursor composition, at present, a high-resolution pattern can be obtained and a composition which can be developed with a basic aqueous solution has not been obtained.

[0007]

SUMMARY OF THE INVENTION The first object of the present invention is to develop an aqueous solution and have excellent photosensitive characteristics, especially excellent in i-line photosensitive characteristics, high sensitivity, and good even at low exposure doses. It is an object of the present invention to provide a photosensitive polyimide precursor composition that can obtain a pattern having an excellent shape, a high residual film ratio after development, and excellent cured film characteristics. A second object of the present invention is to provide, in addition to the above objects, a photosensitive polyimide precursor composition having excellent developability in an aqueous solution. A third object of the present invention is to develop a pattern which is developable with an aqueous liquid and has excellent photosensitive characteristics, particularly excellent i-line photosensitive characteristics, high sensitivity, and a good shape even at a low exposure dose. It is an object of the present invention to provide a pattern manufacturing method capable of obtaining a cured film having a high residual film ratio and excellent cured film characteristics, further reducing the production steps, and reducing the production cost.

[0008]

SUMMARY OF THE INVENTION The present invention is a photosensitive polyimide precursor composition containing a photosensitive polyimide precursor having a photosensitive group and an acidic group, and a photosensitive agent.
The present invention relates to a photosensitive polyimide precursor composition in which a film formed by coating and drying the composition has a dissolution rate in a basic aqueous solution of 0.01 to 0.5 μm / sec.

In the present invention, the photosensitive polyimide precursor is represented by the general formula (1):

Embedded image (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 containing a photosensitive group, A is an acidic group, n represents 1 or 2.) The photosensitive polyimide precursor composition has a repeating unit represented by the following formula: The basic aqueous solution is preferably a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. The photosensitive polyimide precursor composition, in addition to the photosensitive polyimide precursor and the photosensitive agent,
It may contain an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure.

[0010] The present invention also relates to a step of forming a film using the photosensitive polyimide precursor composition, a step of irradiating the film with light through a mask having a predetermined pattern, and a step of irradiating the film after the light irradiation. , The dissolution rate of the non-light irradiated part is 0.01 to
The present invention relates to a pattern manufacturing method including a step of developing using a basic aqueous solution of 0.5 μm / sec.

Further, the present invention relates to the above-described pattern manufacturing method, wherein the irradiation light is i-line.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive polyimide precursor composition of the present invention has a dissolution rate in a basic aqueous solution of a film (prebaked film) formed by coating and drying the composition.
It is important that the thickness be 1 to 0.5 μm / sec, which indicates that the excellent pattern formability of the present invention is exhibited. The dissolution rate is 0.02-0.3 μm / sec
Is preferred. When the dissolution rate is less than 0.01 μm / sec, the solubility of the unexposed portion is low, so that the solubility difference between the unexposed portion and the exposed portion is small, and a good pattern cannot be obtained. On the other hand, if the dissolution rate exceeds 0.5 μm / sec, the exposed portions swell and the pattern shape is poor. Here, the dissolution rate is 20 to 25 ° C.
Is preferably measured at 23 ° C., and particularly preferably measured at 23 ° C. The basic aqueous solution used for measuring the dissolution rate is preferably an aqueous solution containing 1 to 5% by weight of sodium hydroxide, potassium hydroxide, sodium silicate, tetramethylammonium hydroxide, etc. Most preferably, it is based on a .38% by weight aqueous solution. The dissolution rate in the present invention can be determined, for example, by applying the photosensitive polyimide precursor composition to a silicon substrate by spin coating, drying it on a hot plate to form a film having a thickness of 10 to 20 μm, and then adding a basic aqueous solution (23 ° C), dip development or paddle development for 10 to 60 seconds, and then immediately rinse with water or the like to stop development, and measure the reduced film thickness due to dissolution.
It can be obtained by dividing by the development time.

The polyimide precursor used in the photosensitive polyimide precursor composition of the present invention has a photosensitive group and an acidic group, so that it can be developed with a basic aqueous solution and has good photosensitivity. Necessary for preparing a polyimide precursor composition.

The polyimide precursor is generally a polyamic acid having a structural unit composed of a tetracarboxylic acid residue and a diamine residue or a derivative thereof. The photosensitive group may be bonded to the tetracarboxylic acid residue. Or 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 not involved in the formation of an amide bond by reaction with a diamine. Utilizing two carboxyl groups, an ester bond, a photosensitive group is introduced through an amide bond or the like, and a polyimide precursor to which an acidic group is bonded as a side chain of the diamine is exemplified. 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 or Before the polyimide in which two carboxyl groups remain as is and a photosensitive group is introduced into the side chain of the diamine residue via an ester bond, an amide bond, an ether bond, an amino bond, or the like. Body, and the like. As a method for introducing a photosensitive group into a side chain of a diamine residue, a hydroxyl group, a carboxyl group, a diamine having a functional group such as an amino group is reacted with a compound having a group reactive with the 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 characteristics and developability in a basic aqueous solution, so that 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 specifically, a polyimide precursor having a repeating unit represented by the general formula (1) is more preferable because of easy production.

In the repeating unit represented by the general formula (1), the tetravalent organic group represented by R ¹ is a residue of a tetracarboxylic acid or a derivative thereof capable of reacting with a diamine to form a polyimide resin. 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, a total of 6 to 3 carbon atoms including an aromatic ring (benzene ring, naphthalene ring, etc.)
It is preferably an organic group of 0. 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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In the photosensitive polyimide precursor, acidic
A group represented by, that is, represented by A in the general formula (1)
The sulfonic acid group (-) is not particularly limited.
SO _ThreeH), a sulfine group (—SO_TwoH), carboxy
Any one of a hydroxyl group (-COOH) and a phenolic hydroxyl group
Is preferable because of good solubility. these
Among them, carboxyl group and hydroxyl group are particularly good soluble
And easy to synthesize polyimide precursors.
Good.

In the general formula (1), the group R ² to which the acidic group A is bonded is preferably a diamine residue capable of forming a polyimide resin by reacting with tetracarboxylic acid or a derivative thereof. From the viewpoints of mechanical properties, heat resistance and adhesiveness of the polyimide film obtained as described above, it is more preferable that the polyimide film is a trivalent or tetravalent organic group having an aromatic ring and having 6 to 30 carbon atoms in total. 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.

[0022]

Embedded image (However, Z is

Embedded image Indicates)

In the photosensitive polyimide precursor, a photosensitive group and a repeating unit represented by the general formula (1) are represented by R
^The group represented by ³ , for example, a group that is eliminated by light irradiation, a group that 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.

Examples of the group having a polymerizable unsaturated double bond include, for example, the following general formula:

Embedded image (However, 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) Organic groups are preferred because they can impart high sensitivity to 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 (each having an alkyl having 1 to 20 carbon atoms) not only realize high sensitivity, but also are easy to synthesize, and thus are suitable for the present invention. It is.

As the polyimide precursor used in the present invention, together with the repeating unit represented by the above general formula (1),
It may include a repeating unit represented by the general formula (2). this is,

Embedded image (Wherein, R ⁸ is a tetravalent organic group, R ⁹ is a divalent organic group,
¹⁰ is a monovalent organic group or a hydroxyl group, which is a structural unit represented by the formula (1), which is different from the repeating unit represented by the general formula (1).

Specific examples of the tetravalent organic group represented by R ⁸ include those similar to the organic group represented by R ¹ , and preferred ones are also the same. Specific examples of the monovalent organic group represented by R ¹⁰ include a group in which the organic group represented by R ³ is bonded via an oxygen atom, and preferred ones are also the same. Other specific examples of the monovalent organic group represented by R ¹⁰ include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and an n-butoxy group, and an aryloxy group such as a benzyloxy group. , An alkylamino group, a dialkylamino group, an anilino group, a toluidino group and the like. In the case of these other specific examples, those having 1 to 20 carbon atoms in total are preferred.

R ⁹ is a divalent organic group, and preferably contains an aromatic ring or silicon from the viewpoints of mechanical properties, heat resistance, adhesiveness and the like of the polyimide film obtained by curing. In the case of those containing an aromatic ring, those having 6 to 30 carbon atoms are preferable,
In the case of those containing silicon, those having silicon atoms having 1 to 10 (poly) siloxane bonds are preferred. When a plurality of repeating units represented by the general formula (2) are present in a molecule, a plurality of R ⁹ may be the same or different.

Preferred examples of R ⁹ are as follows.

Embedded image

[0030]

Embedded image

[0031]

Embedded image

In the polyimide precursor of the present invention, the ratio of the repeating units represented by the general formulas (1) and (2) is 10 to 10% by mole of each repeating unit.
100 mol%, (2) being 90 to 0 mol%,
It is preferable because the balance between developability in a basic aqueous solution and a good pattern shape is excellent, and it is more preferable that (1) is 80 to 100 mol% and (2) is 20 to 0 mol%.

The polyimide precursor side chain, ie, R ³
And ¹⁰ to 100 mol% of the total group represented by R10 and R10 is preferably a photosensitive group. When having a group other than the photosensitive group, such a group is, 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,
-Butyl groups are particularly preferred.

The molecular weight of the polyimide precursor in the present invention is preferably from 10,000 to 200,000 in terms of weight average molecular weight, from the viewpoint of the properties of the cured film after imidization.
000-50,000 is more preferable. The weight average molecular weight is determined by gel permeation chromatography (G
PC) 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. It can be synthesized by a method of reacting with a diamine, a method of reacting the tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent, or the like.

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 (2,3- or 3,4-dicarboxyphenyl) propane, {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, the following general formula (3)

Embedded image (Wherein, R ¹¹ and R ¹² each represent a monovalent hydrocarbon group, and may be the same or different, and s is an integer of 1 or more). And the like, and 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 (1) is preferable.

The diamine providing the diamine residue R ² in the repeating unit represented by the general formula (1) includes 3,
5-diaminobenzoic acid, 4,4'-dihydroxy-3,
3'-diaminobiphenyl, 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'-diaminodiphenylether, 3,3'-dicarboxy-4,4'-diaminodiphenylether, 3-carboxy-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4, 4 '
-Diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3 ', 5,5'
-Tetracarboxy-4,4'-diaminobiphenyl,
3-carboxy-4,4'-diaminodiphenylsulfone, 3,3'-dicarboxy-4,4'-diaminodiphenylsulfone, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-carboxy-4-aminophenyl) propane and the like.

As the diamine giving the diamine residue R ⁹ in the repeating unit represented by the general formula (2),
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-xylylenediamine, m-xylylenediamine, o-tolidine, o-tolidine sulfone ,
4,4'-methylene-bis- (2,6-diethylaniline), 4,4'-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene,
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'-tetramethyl-4, 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 providing a diamine residue R ⁹ in the repeating unit represented by the general formula (2), the following general formula (4)

Embedded image(Where R¹³And R¹⁴Represents a divalent hydrocarbon group,
Each may be the same or different;^FifteenAnd R¹⁶Is univalent
Which is the same or different
Often, t is an integer of 1 or more)
Diamines such as polysiloxanes can also be used.
R ¹³And R¹⁴As methylene, ethylene,
Arylene such as alkylene group such as pyrene group and phenylene group
And a bonding group thereof.^FifteenAnd R ¹⁶When
Alkyl groups such as methylene group and ethylene group,
And an aryl group such as a nyl group. Using these
1 to 30 mol% based on all amine components
Is preferred.

Further, as a diamine giving a diamine residue R ⁹ in the repeating unit represented by the general formula (2),
In order to improve heat resistance, 4,4'-diaminodiphenylether-3-sulfonamide, 3,4'-diaminodiphenylether-4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide,
Diamine compounds having a sulfonamide group or a carboxide group such as 4'-diaminodiphenyl ether-3-carboxide, 3,4'-diaminodiphenyl ether-3'-carboxide, and 3,3'-diaminodiphenyl ether-4-carboxide Can also be used. When these are used, 1 to all amine components
Preferably, it is used in an amount of up to 30 mol%.

These diamines providing the diamine residue R ⁹ in the repeating unit represented by the general formula (2) are used alone or in combination of two or more.

In the photosensitive polyimide precursor composition of the present invention, since the dissolution rate can be adjusted appropriately and good photosensitive characteristics can be provided, an addition polymerizable compound having a boiling point of 100 ° C. or more at normal pressure is used. Preferably, it is included. If the boiling point is lower than 100 ° C. at normal pressure, the addition-polymerizable compound tends to volatilize and deteriorate its properties when the solvent contained in the system is removed by drying or the like or when irradiated with actinic rays. 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 more at normal pressure include polyhydric alcohols, α, β
A compound obtained by condensing an unsaturated carboxylic acid (for example, ethylene glycol di (meth) acrylate (meaning diacrylate or dimethacrylate, the same applies hereinafter);
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, dimethylaminoethyl (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.), styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone , 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, neopentylglycol di (meth) acrylate, Pentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolpropanetetra (meth)
Acrylates and the like are preferred, and these are used alone or in combination of two or more. When these are used, it is preferable to mix 1 to 100 parts by weight with respect to 100 parts by weight of the polyimide precursor, and 3 to 5 parts by weight.
A range of 0 parts by weight is more preferred. If the amount is outside the range of 1 to 100 parts by weight, the desired effect tends to decrease, and the developing effect tends to be adversely affected.

The photosensitive polyimide precursor composition of the present invention always contains a photosensitive agent. Photo initiators as photosensitizers,
Sensitizers and photoinitiator auxiliaries are mentioned. Adjustment of the dissolution rate in the present invention can be performed by selecting the type and amount of the photosensitive agent together with the type of the polyimide precursor.

The photoinitiator is preferably an aromatic imidazole compound or a titanocene compound. Specific compounds include 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-pyrrole-
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- (pyrrol-1-yl) phenyl] titanium, bis (cyclo Pentadienyl) -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 (cyclopentane Dienyl)
-Bis [2,6-difluoro-3- (2,5-bisdimethylaminopyrrol-1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2 5-dimethyl-3-methoxypyrrole-
1-yl) phenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-methoxyphenyl] titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3-iso Propoxyphenyl)
Titanium, bis (cyclopentadienyl) -bis [2,6
-Difluoro-3-n-propoxyphenyl] titanium and the like. These are used alone or in combination of two or more.

The content of the photoinitiator in the composition is preferably 0.1 to 15.0 parts by weight, and more preferably 0.3 to 8.0 parts by weight based on 100 parts by weight of the polyimide precursor. Is more preferable.

As the sensitizer and the photoinitiating aid, aromatic mercapto compounds and coumarin compounds are preferred. Specific aromatic mercapto compounds include those having one or two mercapto groups having benzene or a heterocycle as a mother nucleus, and in the case of disubstitution, one of the mercapto groups is alkyl or aralkyl. Alternatively, it may be phenyl-substituted, and may be a dimer or disulfide in the form of an intervening alkylene group. Specific sensitizers and photoinitiating assistants include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethyl Anthraquinone, 4,4'-bis (PN, N-diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,2
-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, 7-N, N-diethylaminocoumarin, 3,3'-carbonylbis (7-N, N
-Diethylamino) coumarin, 3,3'-carbonylbis (7-N, N-dimethoxy) coumarin, 3-thienylcarbonyl-7-N, N-diethylaminocoumarin,
-Benzoylcoumarin, 3-benzoyl-7-N, N-
Methoxycoumarin, 3- (4'-methoxybenzoyl)
Coumarin, 3,3'-carbonylbis-5,7- (dimethoxy) coumarin, benzalacetophenone, 4'-
N, N-dimethylaminobenzalacetophenone, 4 '
-Acetaminobenzal-4-methoxyacetophenone and the like. These are used alone or in combination of two or more.

The content of the sensitizer or the photoinitiating auxiliary in the composition is 0.1 to 100 parts by weight of the polyimide precursor.
It is preferably 15.0 parts by weight, and 0.1 to 5.0 parts by weight.
It is more preferred to be parts by weight.

The photosensitive polyimide precursor composition of the present invention may contain other additives, for example, additives such as an organic solvent, a plasticizer, and an adhesion promoter.

Examples of the organic solvent 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, N-acetyl-2-pyrrolidone, N-benzyl-2
-Pyrrolidone, γ-butyrolactone, dimethylsulfoxide, ethylene carbonate, propylene carbonate, sulfolane, hexamethylenephosphortriamide,
Preferred examples include N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. These may be used alone or as a mixed system. Although the content of the organic solvent in the composition is not particularly limited, the polyimide precursor 10
The amount is preferably 100 to 300 parts by weight, more preferably 150 to 200 parts by weight, based on 0 parts by weight. In the composition of the present invention, the dissolution rate is adjusted by using a photosensitive polyimide precursor, a photosensitizer, and an addition polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure,
It can be achieved by appropriately selecting the type and amount of other additives. By using a composition having a dissolution rate defined in the present invention, a good pattern can be produced.

In the pattern production method of 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 the surface of a supporting substrate. 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 the film with light (usually using ultraviolet light) through a photomask having 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 forming method of the present invention, in order to obtain a good pattern, a basic aqueous solution having a dissolution rate of 0.01 to 0.5 μm / sec in a non-light-irradiated portion (unexposed portion) is used as a developing solution. Used. The developer may be an aqueous solution of one compound as long as the aqueous solution exhibits basicity.
An aqueous solution of one or more compounds may be used. The basic aqueous solution is usually a solution in which a basic compound is dissolved in water. The concentration of the basic compound is usually from 0.1 to 50% by weight, but from 0.1 to 30% by weight due to the influence on the supporting substrate and the like.
It is preferable to set the weight%. In addition, the developer is methanol, ethanol, propanol, isopropyl alcohol, N- to improve the solubility of the polyimide precursor.
A water-soluble organic solvent such as methyl-2-pyrrolidone and N, N-dimethylacetamide may be further contained.

The basic compound includes, for example, 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, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, Sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, aminoethanol, 2-aminoethanol, 3-aminopropanol, 2- Aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, Methylamine, triethylamine, tripropylamine, it is preferable to use such triisopropylamine, soluble in water, as long as the aqueous solution exhibits basicity, may be used other than these compounds. Among these, an aqueous solution containing 1 to 5% by weight of tetramethylammonium hydroxide, particularly an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide is frequently used, and is preferable because a good pattern can be formed.

The relief pattern formed by the 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., the pattern made of the polyimide of the present invention can be obtained with high resolution. This pattern has high heat resistance and excellent mechanical properties.

[0060]

The present invention will be described below with reference to examples.

Examples 1 to 3 and Comparative Examples 1 and 2 (1) Synthesis of Polyimide Precursor Synthesis of acid chloride 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.

Synthesis of Polyimide Precursor (Polyamic Acid Ester) In a separate 200 ml four-necked flask, 4.72 g (0.031 mol) of 3,5-diaminobenzoic acid and 5.35 g of pyridine were added.
06 g (0.064 mol), t-butyl catechol 0.
03 g, N-methyl-2-pyrrolidone (NMP) 50 m
The acid chloride solution obtained above was slowly added dropwise over 1 hour while the flask was cooled with ice and stirred (maintaining 10 ° C. or lower). 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 was measured by gel permeation chromatography (GPC) and found to be 44 in terms of polystyrene.
000.

(2) Preparation of Polyimide Precursor Composition 10 g of the obtained polymer was dissolved in 16 g of γ-butyrolactone and 2 g of cyclopentanone, and 2.5 g of tetraethylene glycol diacrylate and a photosensitive agent shown in Table 1 were blended. Thereafter, the solution 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) Measurement of Dissolution Rate of Film The photosensitive polyimide precursor composition prepared in the above (2) is spin-coated on a silicon wafer, and heated at 83 ° C. for 100 seconds and 98 ° C. using a hot plate. The resin film having a thickness of 13 to 14 μm was obtained by heating and drying for 100 seconds. This is 23
The film was developed by immersion in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 30 ° C. for 30 seconds, and immediately thereafter rinsed with water to stop the development. The remaining film thickness was measured, and the difference from the film thickness before development was divided by the development time to determine the dissolution rate.
Table 1 shows the dissolution rates. (4) Formation of Pattern The photosensitive polyimide precursor composition prepared in the above (2) was spin-coated on a silicon wafer and heated on a hot plate at 80 ° C. for 200 seconds to obtain a 15 μm thick coating film.
After this coating film was exposed with an i-line stepper (300 mJ / cm ² ), immersion development was carried out with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Further rinse with water. The pattern shape after development was measured and observed, and the resolution and pattern shape are shown in Table 1.

[0065]

[Table 1]

Examples 4 to 6 Using the patterns obtained in Examples 1 to 3, under 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 better photosensitive characteristics than the composition of the comparative example.

[0067]

The photosensitive polyimide precursor composition of the present invention can be developed with an aqueous solution, has excellent photosensitive properties, particularly excellent i-line photosensitive properties, has high sensitivity, and has good sensitivity even at low exposure doses. A shape pattern is obtained, the residual film ratio after development is high, and the cured film characteristics are excellent. The composition containing the photosensitive polyimide precursor having the structural unit represented by the general formula (1) has excellent developability in an aqueous solution in addition to the above effects. The pattern manufacturing method of the present invention can be developed with an aqueous liquid, and has excellent photosensitive characteristics, particularly excellent i-line photosensitive characteristics, high sensitivity, and a pattern having a good shape even at a low exposure dose. Has a high residual film ratio, and a cured film having excellent cured film characteristics can be obtained. Further, the production process can be shortened, and the production cost can be reduced.

Claims (6)

[Claims] 1. A photosensitive polyimide precursor composition comprising a photosensitive polyimide precursor having a photosensitive group and an acidic group and a photosensitive agent, wherein the composition is formed by coating and drying the composition. The dissolution rate in a basic aqueous solution is 0.01
A photosensitive polyimide precursor composition having a viscosity of about 0.5 μm / sec. 2. The photosensitive polyimide precursor represented by the general formula (1): (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 containing a photosensitive group, A is an acidic group, The photosensitive polyimide precursor composition according to claim 1, wherein the photosensitive polyimide precursor composition has a repeating unit represented by the following formula: 3. The method according to claim 1, wherein the basic aqueous solution is a 2.38% by weight aqueous solution of tetramethylammonium hydroxide.
The photosensitive polyimide precursor composition as described in the above. 4. The photosensitive polyimide precursor composition according to claim 1, further comprising an addition polymerizable compound having a boiling point of 100 ° C. or higher at normal pressure. 5. A step of forming a film using the photosensitive polyimide precursor composition according to claim 1, 2, 3, or 4, irradiating the film with light through a mask having a predetermined pattern; A pattern manufacturing method comprising a step of developing a film after light irradiation using a basic aqueous solution having a dissolution rate of a non-light irradiated portion of 0.01 to 0.5 μm / sec. 6. The pattern manufacturing method according to claim 5, wherein the irradiation light is an i-line.