JPH10158397A - Polyimide precursor, its production, polyimide, its production and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide precursor comprising a specific repeating unit, having an excellent image-forming property, further capable of expressing excellent mechanical characteristics, excellent heat resistance, excellent adhesivity and low thermal expansion after thermally cured, and useful as a heat-resistant photo-sensitive material in the fields of semiconductor-integrated circuits, etc. SOLUTION: This polyimide precursor comprises (A) a repeating unit of formula I [R<1> is a tetravalent organic group; R<2> is a divalent organic group; X, X' are each OH, a group of the formula: O-R (R is double bond-containing group, a 1-3C alkyl), a group of the formula: NH-R' (R' is R), a group of the formula: O<-> .<+> NR'' (R'' is R; Z is H, a 1-3C alkyl)] and (B) a repeating unit of formula II [Y is a group of formula III (R<3> , R<4> are each a divalent organic group such as (substituted) m- or p-phenylene)] in an A/B molar ratio of e.g. 10/90 to 98/2. The compound is obtained by reacting a compound of formula IV with a compound of the formula: H2 N-R<2> -NH2 and a compound of the formula: H2 N-R<3> -CO-NH-R<4> -NH2 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyimide precursor, a method for producing the same, a polyimide, a method for producing the same, and a photosensitive resin composition.

[0002]

2. Description of the Related Art In recent years, formation of a circuit pattern on a semiconductor integrated circuit or a printed circuit board is performed by forming a resist material on a base material surface, removing unnecessary portions by exposing or etching predetermined portions, and cleaning a substrate surface. Since pattern formation is performed through a variety of complicated processes such as exposure, development of a heat-resistant photosensitive material that can use a necessary portion of the resist as an insulating material even after pattern formation by exposure and development is desired. I have. As these materials, for example, photosensitive polyimides, heat-resistant photosensitive materials using cyclized polybutadiene or the like as a base polymer have been proposed, and in particular, photosensitive polyimides have excellent heat resistance and can easily remove impurities. Particular attention has been paid to this fact.

[0003] As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No. 49-17374) was first proposed. While having the advantages of high sensitivity and high film-forming ability, it lacks storage stability and has drawbacks such as chromium ions remaining in polyimito,
It did not reach practical use. In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (JP-A-54-109828),
A method has been proposed in which a functional group in a polyimide precursor is reacted with a functional group of a compound having a photosensitive group to impart a photosensitive group (JP-A-56-24343, JP-A-60-100143, and the like). I have.

However, these photosensitive polyimide precursors use an aromatic monomer having excellent heat resistance and mechanical properties as a basic skeleton, and have excellent heat resistance and mechanical properties.
Adhesion, low thermal expansion, etc. are inferior, and none of them has a well-balanced performance. On the other hand, in the field of printed circuit boards, etc., polyimide is widely used due to its excellent heat resistance and mechanical properties, but its thermal expansion coefficient is large, so its thermal dimensional stability is poor. However, there is a problem that the temperature decreases and warpage occurs.

[0005]

The invention according to claims 1 to 3 has excellent image forming properties and excellent mechanical properties after thermosetting.
An object of the present invention is to provide a polyimide precursor having heat resistance, adhesiveness, and low thermal expansion. The invention according to claim 4 or 5 provides a method for producing the above polyimide precursor. The invention according to claim 6 has excellent mechanical properties, heat resistance,
An object of the present invention is to provide a polyimide having adhesiveness and low thermal expansion property. The invention according to claim 7 provides a method for producing the above polyimide. The invention according to claim 8 is
Excellent image forming properties, excellent mechanical properties after heat curing, heat resistance,
An object of the present invention is to provide a photosensitive resin composition having an adhesive property and a low thermal expansion property.

[0006]

The present invention provides a compound represented by the general formula (I):

Embedded image (Wherein, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, and X and X ′ each independently represent —OH, —O—
R, -NH-R ', - O - · + NR " indicates a Z _3, R,
R ′ and R ″ are a group having a polymerizable double bond or an alkyl group having 1 to 3 carbon atoms;
Wherein three Z's may be the same or different) and a repeating unit represented by the general formula (II)

Embedded image (Where Y is

Embedded image (Wherein, R ³ and R ^{4 each} represent a divalent organic group).
¹ , X and X 'are the same as in the general formula (I)).

The above R ¹ typically corresponds to a residue of tetracarboxylic acid which is a raw material of polyimide. In addition, the above R ² typically corresponds to a residue of a diamine serving as a raw material of a polyimide.

According to the present invention, in these polyimide precursors, R ³ and R ⁴ in the general formula (II) are each independently a metaphenylene group or a paraphenylene group which may have a substituent. About something. The present invention also relates to these polyimide precursors represented by the general formula (I)
The repeating unit represented by the formula (II) and the repeating unit represented by the general formula (II) are represented by a molar ratio of 10/90 to 9/9.
8/2.

The present invention also relates to a compound of the formula (III)

Embedded image (Wherein R ¹ , X and X ′ have the same meanings as in the general formula (I)) and a derivative thereof represented by the general formula (IV)

Embedded image (Wherein, R ² has the same meaning as in formula (I))
And a diamine represented by the formula (V):

Embedded image (Wherein R ³ and R ⁴ have the same meanings as in the general formula (II)).

The present invention also relates to a method for producing a polyimide precursor, wherein the diamine represented by the general formula (IV) and the diamine represented by the general formula (V) are mixed in a molar ratio of 10/90 to the former / the latter. The present invention relates to a method for producing a polyimide precursor to be blended so as to be 98/2.

The present invention also relates to a compound represented by the general formula (VI):

Embedded image (Wherein R ¹ and R ² are the same as in the general formula (I)) and the general formula (VII)

Embedded image (Where Y is

Embedded image (Wherein, R ³ and R ^{4 each} represent a divalent organic group).
¹ represents a tetravalent organic group). The present invention also relates to a method for producing a polyimide, characterized in that any one of the polyimide precursors is subjected to imide ring closure. The present invention also provides
The present invention relates to a photosensitive resin composition containing any one of the polyimide precursors and an addition polymerizable compound.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The general formulas (I) and (III)
In the above, R, R ′ and R ″ represent a 2-acryloyloxyethyl group, a 2-methacryloyloxyethyl group, a 2- (1-acryloyloxy) propyl group,
And (1-methacryloyloxy) propyl, 2-hydroxy-3-acryloyloxypropyl, 2-hydroxy-3-methacryloyloxypropyl, acrylaminomethyl and the like. General formula (I), General formula (II)
And in formula (III), one of CO-X and two azide bonds or carboxyl groups and the other of CO-X 'and two azide bonds or carboxyl groups are bonded to adjacent carbon atoms at R ¹ . Or are bound to the peri position.

The polyimide precursor of the present invention has a repeating unit represented by the general formula (I), and when X or X 'in the general formula (I) is a group having a polymerizable double bond. The polyimide precursor has photopolymerizability (photosensitivity). In this case, it is preferable to use a mixture with the addition polymerizable compound. Further, the polyimide precursor of the present invention has a repeating unit represented by the general formula (I). Even when X or X ′ in the general formula (I) is not a group having a polymerizable double bond, It has photopolymerizability (photosensitivity) when used by being mixed with an addition polymerizable compound.

The polyimide precursor of the present invention has a repeating unit represented by the general formula (I), wherein R, R 'or R "in the general formula (I) is an alkyl group having 1 to 5 carbon atoms. And a hydrocarbon group such as a phenyl group and a cyclohexyl group (referred to as general formula (I ')).

The polyimide precursor of the present invention has the general formula (II)
A tetracarboxylic acid or a derivative thereof represented by I) and a diamine represented by general formula (IV) and general formula (V):
It can be synthesized by reacting in an organic solvent used as necessary using a known method.

Examples of the tetracarboxylic acid derivative represented by the general formula (III) include tetracarboxylic dianhydride and tetracarboxylic acid chloride. Examples of the tetracarboxylic acid include 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, 3,4,9,1
0-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-dicarboxidiphenyl) propane, 2,2-bis (2,3-1 or 3,4-dicarboxidiphenyl ) 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, the following general formula (VIII)

Embedded image (Wherein, R ⁶ and R ⁷ represent a monovalent hydrocarbon group such as a phenyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an alkyl group having 1 to 5 carbon atoms, Each of which may be the same or different, and n is an integer of 1 to 100), such as an aromatic tetracarboxylic acid such as a tetracarboxylic acid represented by the formula: You.

The diamine represented by the general formula (IV) is not particularly limited as long as it can be used as a raw material for polyimide. For example, 4,4 '-(3,4'
-, 3,3'-, 2,4'- or 2,2 '-) diaminodiphenyl ether), 4,4'-(3,4 '-, 3,
3'-, 2,4'- or 2,2'-) diaminodiphenylmethane, 4,4 '-(3,4'-, 3,3'-, 2,
4'- or 2,2'-) diaminodiphenyl sulfone,
4,4 '-(3,4'-, 3,3'-, 2,4'- or 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), , 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'-tetramethyl-4,4'-diaminodiphenylmethane, bis [4- (3'-aminophenoxy) phenyl] sulfone, 2,2-bis (4-aminophenyl) propane and the like. Is alone or 2
A combination of more than one type can also be used.

The following general formula (IX)

Embedded image (Wherein R ⁸ and R ⁹ are a phenylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, 1 to 3 carbon atoms)
Represents a divalent hydrocarbon group such as an alkylene group, which may be the same or different, and R ¹⁰ and R ^{11 each} have 1 carbon atom.
A monovalent hydrocarbon group such as a phenyl group which may have 1 to 3 alkyl groups as a substituent, an alkyl group having 1 to 5 carbon atoms, which may be the same or different, and m is 1 or more And an aliphatic diamine such as diaminopolysiloxane represented by the following formula:

The diamine represented by the general formula (V) is not particularly limited, and includes, for example, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide,
4,3'-diaminobenzanilide and the like can be mentioned, and these can be used alone or in combination of two or more. The use amount of the diamine represented by the general formula (V) is preferably in the range of 2 to 90 mol%, more preferably in the range of 5 to 85 mol% of the total amount of the diamines. If the amount is too small, the adhesiveness and low thermal expansion tend to decrease, while if it is too large, the translucency tends to decrease.

As the organic solvent used for the production of the polyimide precursor, a polar solvent which completely dissolves the polyimide precursor to be purified is preferable, for example, N-methyl-2-pyrrolidone, N, N-dimethyl-acetamide, N, N-
Examples include dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, and γ-butyrolactone. Further, in addition to this polar solvent, ketones, esters, lactones, ethers,
Halogenated hydrocarbons, hydrocarbons and the like can also be used, for example, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl malonate Ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, hexane, hebutane, octane, benzene, toluene, xylene, p
-Cymene and the like. These organic solvents can be used alone or in combination of two or more.

In the polyimide precursor of the present invention, when X and X 'contain a group other than OH, the diamine compound is reacted with a tetracarboxylic dianhydride, a tetracarboxylic acid chloride or the like by the method described above. To the polyimide precursor obtained by the general formula (X)

Embedded image (Wherein R is the same as described above), a compound having a glycidyl group and a polymerizable double bond such as glycidyl acrylate and glycidyl methacrylate,
General formula (XI)

Embedded image Wherein R ′ is the same as defined above, represented by general formula (XII):

Embedded image Wherein R ″ and Z are the same as described above, and two Zs may be the same or different.
It can also be produced by reacting methacryloxyethyltrimethylammonium hydroxide by a known method.

Examples of the alcohol compound represented by the general formula (X) include 2-hydroxyethyl methacrylate and 3-hydroxyethyl methacrylate.
Hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-
And hydroxypropyl acrylate. Examples of the amine compound represented by the general formula (XI) include 2-amino-3
-Aminopropyl methacrylate, 2-aminopropyl methacrylate, 2-aminoethyl acrylate, 3-
Examples include aminopropyl acrylate and 2-aminopropyl acrylate.

Examples of the amine compound represented by the general formula (XII) include N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate,
N, N-dimethylaminopropyl methacrylate, N,
N-diethylaminopropyl methacrylate, N, N-
Dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminoethyl acrylamide, etc. Can be These are used to form addition salts with carboxyl groups.

The polyimide of the present invention can be synthesized by subjecting the polyimide precursor to imide ring closure. In the general formulas (VI) and (VII), the two carbonyl groups forming the imide ring are bonded to adjacent carbon atoms or peri positions in R ¹ . The imide ring closure can be usually performed by heating. The heating conditions are not particularly limited, but the heating temperature is 80 to 4
The temperature is preferably set to 50 ° C. The heating temperature is 80 ° C
If the temperature is less than 450 ° C., the ring closure reaction tends to be slow, and if it exceeds 450 ° C., the produced polyimide tends to deteriorate.
The heating time is preferably set to 10 to 100 minutes. If the heating time is less than 10 minutes, the ring-closing reaction tends not to proceed sufficiently. If the heating time exceeds 100 minutes, the resulting polyimide tends to deteriorate, and the workability tends to decrease.

A photosensitive resin composition can be prepared using the above polyimide precursor. When the polyimide precursor does not have photosensitivity, photosensitivity is imparted by mixing an addition polymerizable compound. The addition-polymerizable compound can be used as a mixture with a photosensitive polyimide precursor.

Examples of such an addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylolpropane. Diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate,
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, penta Erythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4
-Vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, Methylenebisacrylamide, N, N-dimethylacrylamide, N-
Methylol acrylamide, triacrylate of tris (β-hydroxyethyl) isocyanurate, triacrylate of tris (β-hydroxyethyl) isocyanurate, the following general formula (XIII)

Embedded image (Wherein, R ¹² represents hydrogen or a methyl group, and O and P represent 1
And the like). These can be used alone or in combination of two or more.

The amount of the addition polymerizable compound used is preferably 1 to 200% by weight based on the polyimide precursor. When the amount is less than 1% by weight, the photosensitive characteristics including solubility in a developing solution tend to be inferior, and when it exceeds 200% by weight, the mechanical characteristics of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention can contain a photoinitiator, if necessary. The photoinitiator is not particularly limited, and examples thereof include Michler's ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 2-ethylanthraquinone,
4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-
Diethylthioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, benzyl, diphenyldisulfide, phenanthrenequinone ,
2-isopropylthioxanthone, riboflavin tetrabutyrate, 2,6-bis (p-diethylaminobenzal) -4-methyl-4-azacyclohexanone, N-ethyl-N- (p-chlorophenyl) glycine, 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, 3,3-carbonylbis (7-diethylaminocoumarin), bis (cyclopentadienyl) -bis-
[2,6-difluoro-3- (pyr-1-yl) phenyl] titanium benzanthrone, 3,3'-dimethoxy-
4,4'-diazidobiphenyl, 3,5-bis (4-diethylaminobenzylidene) -1-methyl-4-asacyclohexanone, 4-methyl-7-diethylaminocoumarin, 4,6-dimethyl-ethylaminocoumarin ,
7-diethylamino-3-thenonylcoumarin, benzyldimethylketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethyl 4-diethylaminobenzoate, 1,3 -Diphenylpropanetrione-2- (o-ethoxydicarbonyl) oxime, N- (4-cyanophenyl) glycine,
1,7-bis (9-aglidinyl) heptane and the like can be mentioned. These can be used alone or in combination of two or more.

The amount of the photoinitiator used is preferably 0.01 to 30% by weight based on the polyimide precursor.
More preferably, the content is 0.05 to 10% by weight. If the amount is less than 0.01% by weight, the light sensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention can contain an azide compound, if necessary. As azide compounds, for example,

Embedded image

Embedded image And the like. These can be used alone or in combination of two or more.

The amount of the azide compound used is preferably 0.01 to 30% by weight based on the polyimide precursor. If the amount is less than 0.01% by weight, the light sensitivity tends to be poor, and if it exceeds 30% by weight, the mechanical properties of the film tend to be inferior.

Further, the photosensitive resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance the stability during storage. As the radical polymerization inhibitor or the radical polymerization inhibitor, for example,
Hydroquinone, hydroquinone monomethyl ether, benzoquinone, diphenyl-p-benzoquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paracinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-1-naphthylamine, N-phenyl-2- Naphthylamine, N-phenyl-2-naphthylamine, cuperon, phenothiazine, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like. These can be used alone or in combination of two or more.

The amount of the radical polymerization inhibitor or the radical polymerization inhibitor used is based on the resin content of the polyimide precursor.
The content is preferably 0.01 to 30% by weight. If the amount is less than 0.01% by weight, the storage stability tends to be inferior, and if it exceeds 30% by weight, the photosensitivity and the mechanical properties of the film tend to be inferior.

The photosensitive resin composition of the present invention is applied onto a base material such as a silicon wafer, a metal substrate, a ceramic substrate or the like by a coating method, an immersion method, a spray method, a screen printing method, or a spin coating method. By heating and drying the portion, a coating film having no tackiness can be obtained. A desired relief pattern can be obtained by irradiating the coating film with actinic rays or actinic rays through a mask on which a desired pattern is drawn, and then dissolving and removing the unirradiated portion with an appropriate developer.

As the actinic ray or actinic ray for irradiating the photosensitive resin composition of the present invention, for example, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, an i-line stepper, a g-line stepper And other ultraviolet rays, visible rays, X-rays, and electron beams. As the developer, for example, a good solvent (N, N-
Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.), a mixed solvent of a good solvent and a poor solvent (lower alcohol, water, aromatic hydrocarbon, etc.), a basic solution (tetramethyl hydroxide) Aqueous solution of ammonium, aqueous solution of triethanolamine), aqueous solution of inorganic alkali, aqueous solution of inorganic alkali containing a solvent, and the like. After the development, if necessary, it is preferable to rinse with water or a poor solvent and dry at room temperature to about 100 ° C. to make the pattern stable.

By heating this relief pattern, a patterned high heat-resistant polyimide can be formed. The heating temperature at this time is 150 to 5
The temperature is preferably set to 00 ° C, more preferably 200 to 400 ° C. If the heating temperature is lower than 150 ° C., the mechanical and thermal properties of the polyimide film tend to decrease, and if it exceeds 500 ° C., the mechanical and thermal properties of the polyimide film tend to decrease. The heating time at this time is preferably set to 0.05 to 10 hours. If the heating time is less than 0.05 hours, the mechanical properties and thermal properties of the polyimide film tend to decrease,
If the time exceeds 10 hours, the mechanical and thermal properties of the polyimide film tend to decrease. Thus, the photosensitive resin composition of the present invention can be used for various protective films, insulating films, and the like.

[0037]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Synthesis Example 1 100 equipped with a stirrer, a cooling pipe, a thermometer and a nitrogen introducing pipe
In a four ml flask, 3.4 g (0.017 mol) of 4,4'-diaminodiphenyl ether, 0.681 g (0.003 mol) of 4,4'-diaminobenzanilide, N
28.223 g of -methyl-2-pyrrolidone and N, N-
28.223 g of dimethylacetamide is charged and dissolved by stirring at room temperature under a nitrogen flow. When 4,4'-diaminodiphenyl ether and 4,4'-diaminobenzanilide are completely dissolved, 5.88 g (0.02 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride is added. After stirring for about 5 hours, a viscous polyimide precursor solution was obtained. Further, this solution was heated at 65 to 70 ° C., and the viscosity was adjusted to 2.0 Pa · s (solid content: 15% by weight) to obtain a polyimide precursor solution (PI-1). The viscosity was measured using an E-type viscometer (EHD type, manufactured by Toki Sangyo Co., Ltd.)
Was measured at a temperature of 25 ° C. and a rotation speed of 10 rpm.

Synthesis Examples 2 to 10 In Synthesis Example 1, the charged amounts of 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzanilide, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are shown in Table 1. Except for using the amounts shown in (1), the same operation as in Synthesis Example 1 was performed to obtain polyimide precursor solutions (PI-2 to PI-10).

[0040]

[Table 1]

The obtained polyimide precursor solution (P
The dried I-1 to PI-9) was subjected to an infrared absorption spectrum (JIR-1 manufactured by JEOL Ltd.) by the KBr method.
00 type), all were 1540 cm ^-1 ,
C = 0 absorption of amide group at around 1650 cm ⁻¹ , 3300
The absorption of N—H was confirmed near cm ⁻¹ .

Example 1 100 ml equipped with a stirrer, a cooling pipe and a thermometer nitrogen introduction pipe
In a flask, 56.4469 of the polyimide precursor solution (PI-1) obtained in Synthesis Example 1, 0.284 g of 2,4-diethylthioxanthone (DETX), and 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
After 0.9979 of -butan-1-one (I-369) was charged and stirred and dissolved, an equivalent of N, N-diethylaminoethyl methacrylate (DEAEM) was added to the carboxyl group of the polyimide precursor, and the mixture was stirred and mixed. The solution,
Filter the solution to obtain a uniform photosensitive resin composition solution (PP
I-1) was obtained.

Example 2 In Example 1, 56.446 g of PI-1 and PI-2
Of the photosensitive resin composition solution (PP)
I-2) was obtained.

Example 3 In Example 1, 56.446 g of PI-1 and PI-3
Was changed to 57.517 g, and the same operation as in Example 1 was performed to obtain a uniform photosensitive resin composition solution (PP
I-3) was obtained.

Example 4 In Example 1, 56.446 g of PI-1 and PI-4
Was carried out in the same manner as in Example 1 except that the content of the photosensitive resin composition solution (PP
I-4) was obtained.

Example 5 In Example 1, 56.446 g of PI-1 and PI-5
Was carried out in the same manner as in Example 1 except that the content of the photosensitive resin composition solution was changed to 56.293 g.
I-5) was obtained.

Example 6 In Example 1, 56.446 g of PI-1 and PI-6
Was carried out in exactly the same manner as in Example 1 except that the amount of the photosensitive resin composition solution was changed to 56.140 g.
I-6) was obtained.

Example 7 In Example 1, 56.446 g of PI-1 and PI-7
Was carried out in the same manner as in Example 1 except that the weight of the photosensitive resin composition was changed to 58.741 g.
I-7) was obtained.

Comparative Example 1 In Example 1, 56.446 g of PI-1 and PI-8
Was carried out in exactly the same manner as in Example 1 except that the amount of the photosensitive resin composition was 56.017 g.
I-8) was obtained.

Comparative Example 2 In Example 1, 56.446 g of PI-1 and PI-9
Was carried out in the same manner as in Example 1 except that the photosensitive resin composition was changed to 58.894 g.
I-9) was obtained.

Comparative Example 3 In Example 1, 56.446 g of PI-1 and PI-1
0 was set to 55.987 g, and the same operation as in Example 1 was performed to obtain a uniform photosensitive resin composition solution (P
PI-10) was obtained.

The obtained photosensitive resin composition solution (PPI-
1 to PPI-10) with stainless steel foil (SUS
304TH-TA, thickness 25 μm). Next, using a hot plate, heated at 90 ° C. for 480 seconds to form a 10 μm coating film, followed by pattern masking,
Exposure was performed with an ultra-high pressure mercury lamp. This was subjected to dip development using a mixed solvent of N-methyl-2-pyrrolidone / water (80/20 (volume ratio)), and this was ripened at 350 ° C. for 60 minutes in a nitrogen atmosphere to form a polyimide relief pattern. Obtained.

Example 8 In a flask similar to that of Example 1, 56.446 g of the polyimide precursor solution (PI-11) obtained in Synthesis Example 1 was added, and DET was added.
0.284 g of X and 0.997 g of I-369 were charged,
After stirring and dissolving, 6.773 g of tetraethylene glycol diacrylate (A-4G) was added, and the solution obtained by stirring and mixing was filtered with a filter to obtain a uniform photosensitive resin composition solution (PPI-11). Was.

Examples 9 to 14 In Example 8, the polyimide precursor solution and A-4
Except that G was as shown in Table 2, the same operation as in Example 8 was performed to obtain photosensitive resin composition solutions (PPI-12 to PPI-17).

[0055]

[Table 2]

Comparative Examples 4 to 6 In Example 8, the polyimide precursor solution and A-4
The same operation as in Example 8 was carried out except that G was as shown in Table 3, respectively, to obtain a photosensitive resin composition solution (P
PI-18 to PPI-20) were obtained.

[0057]

[Table 3]

The obtained photosensitive resin composition solution (PPI-
11 to PPI-20) with stainless steel foil (SU
S304TH-TA, thickness 2511 m).
Next, the film was heated at 90 ° C. for 480 seconds using a hot plate to form a 10 μm coating film, and then subjected to pattern masking and exposure with an ultra-high pressure mercury lamp. This is dip-developed using an inorganic alkali aqueous solution containing diethylene glycol monobutyl ether / water (95/5 (volume ratio)) and sodium tetraborate decahydrate 10 g / l as a solvent, and then subjected to dip development under a nitrogen atmosphere. Heat at 350 ° C for 60 minutes,
A polyimide relief pattern was obtained.

When an infrared absorption spectrum of a part of the obtained polyimide relief pattern was measured by the KBr method, characteristic absorption of imide was confirmed at around 1780 cm ^-1 . Each of the polyimide precursor solutions (PI-1 to PI-10) obtained in Synthesis Examples 1 to 10 was applied, and 90 ° C.
The coating film obtained by drying for 480 seconds was measured with a spectrophotometer (wavelength: 400 nm). The resolution was evaluated using a line / space test pattern as the minimum size of a developable line / space.

The heat loss starting temperature is determined by applying a photosensitive resin composition solution (PPI-1 to PPI-20) on a glass plate,
After drying at 90 ° C for 480 seconds, under nitrogen atmosphere at 350 ° C
The coating film (thickness: 5 μm) obtained by heating for 60 minutes was measured by 951-TGA manufactured by TA-Isstrument. Atmosphere: Air 200 ml / min Heating rate: 10 ° C./min The glass transition point and the coefficient of thermal expansion were determined by applying a photosensitive resin composition solution (PPI-1 to PPI-20) on a glass plate,
After drying at 90 ° C for 480 seconds, under nitrogen atmosphere at 350 ° C
The coating film (film thickness: 10 μm) obtained by heating at 60 ° C. for 60 minutes was measured with TMA-120 manufactured by Seiko Instruments Inc. Atmosphere: air Heating rate: 5 ° C / load Load: 10g

The adhesive property was determined by using a photosensitive resin composition solution (PPI
-1 to PPI-20) with stainless steel foil (SUS304T)
H-TA, thickness 251 μm)
After drying for 0 second, the coating film (film thickness: 10 μm) obtained by heating at 350 ° C. for 60 minutes in a nitrogen atmosphere was subjected to a pressure tucker test (conditions: 121 ° C., 2.0265 × 1).
0 ⁵ Pa, 300 hours) were evaluated by the cross-cut adhesion test after performing the. In addition, the cross cut test is 10 mm at 1 mm with a cutter knife.
Make a scratch on the grid so that there are 0 squares, and peel it off with cellophane tape in accordance with JIS (JIS K 5400). It is a method of expressing. The evaluation results are shown in Tables 4 and 5.

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

The polyimide precursor according to any one of claims 1 to 3 is excellent in adhesiveness and low thermal expansion property, and has a buffer coat film for semiconductor integrated circuits, an interlayer insulating film for MCM, a circuit protective film on various substrates, and a salter resist. And so on. The preferred polyimide precursor can be produced by the method for producing a polyimide precursor according to claims 4 and 5.
The polyimide according to claim 6 is excellent in film adhesiveness and low thermal expansion property. The polyimide can be produced by the method for producing a polyimide according to the seventh aspect. The photosensitive resin composition according to claim 8 is excellent in image forming property, and a polyimide pattern obtained by the photosensitive resin composition is:
Excellent mechanical properties, heat resistance, adhesiveness, and low thermal expansion.

Claims (8)

[Claims] 1. A compound of the general formula (I) (Wherein, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group, and X and X ′ each independently represent —OH, —O—
R, -NH-R ', - O - · + NR " indicates a Z _3, R,
R ′ and R ″ are a group having a polymerizable double bond or an alkyl group having 1 to 3 carbon atoms;
Wherein the three Z's may be the same or different) and a repeating unit represented by the general formula (II): (Where Y is (Wherein, R ³ and R ^{4 each} represent a divalent organic group).
¹ , X and X 'are the same as in the general formula (I)). 2. The polyimide precursor according to claim 1, wherein R ³ and R ⁴ in the general formula (II) are each independently a metaphenylene group or a paraphenylene group which may have a substituent. 3. The method according to claim 1, wherein the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) are contained in a molar ratio of 10/90 to 98/2. Item 3. The polyimide precursor according to Item 1 or 2. 4. A compound of the general formula (III) (Wherein R ¹ , X and X ′ have the same meanings as in the general formula (I)) and a derivative thereof represented by the general formula (IV): (Wherein, R ² has the same meaning as in formula (I))
And a diamine represented by the general formula (V): (Wherein R ³ and R ⁴ have the same meanings as in the general formula (II)). 5. The compound according to claim 4, wherein the diamine represented by the general formula (IV) and the diamine represented by the general formula (V) are blended so that the former / latter has a molar ratio of 10/90 to 98/2. A method for producing a polyimide precursor. 6. A compound of the general formula (VI) (Wherein, R ¹ represents a tetravalent organic group, and R ² represents a divalent organic group) and a repeating unit represented by the general formula (VII): (Where Y is (Wherein, R ³ and R ^{4 each} represent a divalent organic group).
¹ represents a tetravalent organic group). 7. A method for producing a polyimide, comprising subjecting the polyimide precursor according to claim 1 to imide ring closure. 8. A photosensitive resin composition comprising the polyimide precursor according to claim 1 and an addition polymerizable compound.