JP2002003516A - Composition and photosensitive composition as well as cover layer film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition and a photosensitive composition as well as a cover layer film composed of the composition which have enough mechanical strengths, excellent heat resistance, processability, adhesion and especially the excellent low hygroscopicity. SOLUTION: There are provided the composition which has at least a soluble polyimide and a compound having C-C double bonds of 2 or more as an essential component, the composition wherein Tg of B stage is -20 to 150 deg.C, Tg after curing is 70 to 300 deg.C, the soluble polyimide has Tg of 100 to 300 deg.C and the thermal expansion coefficient after curing is 20 to 500 ppm and the photosensitive polyimide composition obtained by adding an epoxy resin and/or a photoreactive initiator or intensifier as essential components to the composition. These are especially useful as a photosensitive composition. These photosensitive polyimide composition is used to provide a cover layer film which has enough mechanical strengths and also has excellent properties in the heat resistance, processability, adhesion and especially low hygroscopicity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, workability,
The present invention relates to a composition having excellent adhesiveness, particularly excellent in low hygroscopicity, and a photosensitive composition and a coverlay film using the same.

[0002]

2. Description of the Related Art In recent years, electronic devices have become increasingly sophisticated, sophisticated, and miniaturized at an extremely high speed. , Weight reduction is required. For this reason, a wiring board on which electronic components are mounted is also more flexible than a normal hard printed wiring board.
C) is gaining attention and demand is rapidly increasing.

In this FPC, a film called a coverlay film made of polyimide or the like is laminated on the circuit surface for the purpose of protecting a conductor surface on which a circuit is formed by a conductor such as a copper foil. As a method for bonding the coverlay film, a method is generally used in which a coverlay film having an adhesive on one side is processed into a predetermined shape, overlapped with an FPC, aligned, and then thermocompressed with a press or the like. It is. However, the adhesives used for these are mainly epoxy-based and acrylic-based adhesives, and have problems such as low heat resistance such as solder heat resistance and adhesive strength at high temperatures, and poor flexibility. Yes, the performance of the polyimide film used as the coverlay film could not be fully utilized.

In addition, when a coverlay film is bonded to an FPC using a conventional adhesive, holes or windows are formed in the coverlay film before bonding, for example, in a joint portion between a terminal portion and a component of a circuit. It had to be processed. However, not only is it difficult to make holes in thin coverlay films, but also
Alignment to a predetermined position of the PC is almost a manual operation, and the workability and positional accuracy are very poor, and the cost is high.

[0005] In order to improve the workability and the positional accuracy of the formed holes, photosensitive dry film resists have been studied. Although the workability and hole positioning accuracy were certainly improved by the dry film resist being studied, the acrylic resin was used, so there was a problem with the heat resistance and the brittleness of the film. ing.

[0006] In view of this situation, the present inventors have solved the above-mentioned conventional problems, and have sufficient mechanical strength.
Excellent heat resistance, further processability, adhesiveness, especially, a result of intensive research aimed at providing a coverlay film made of a photosensitive composition excellent in low moisture absorption, the present invention was reached. .

[0007]

The first aspect of the present invention is to provide a composition comprising at least a soluble polyimide and a compound having two or more carbon-carbon double bonds as essential components. A. Soluble polyimide: 100 parts by weight, B.I. An acryloyl group or a methacryloyl group, a vinyl group, a compound containing two or more organic groups selected from an allyl group: a composition having 1 to 150 parts by weight as an essential component, the third of the present invention is the soluble polyimide, 1 to aromatic ring
The composition obtained by using an acid dianhydride having three or an alicyclic acid dianhydride, a fourth composition of the present invention, wherein the soluble polyimide is a diamine having 1 to 6 aromatic rings, or According to a fifth aspect of the present invention, there is provided a composition obtained by using a diamine having a siloxane bond in an amount of 5 to 100 mol% based on all diamines,

Embedded image (Wherein, R ¹ represents —, —CO—, —O—, —C (CF ₃ )
_{2 -, - C (CH 3} ) 2 - a, R ² represents a divalent organic group. The present invention provides a composition obtained by using an acid dianhydride selected from the above) in an amount of 10 to 100 mol% based on the total acid dianhydride.

Embedded image (Wherein, R ³ is —, —CO—, —O—, —C (CF ₃ )
_{2 -, - C (CH 3} ) 2 -, - COO- a, R ⁴ is hydrogen,
A halogen, a methoxy group, a C1-C5 alkyl group
Represents 0, 1, 2, 3 and n represents 0, 1, 2, 3, 4. ) Is selected from 10 to 10
The composition obtained by using 100 mol% is the seventh composition of the present invention.
Is a compound represented by the general formula (1):

Embedded image (Where R ⁵ is a tetravalent organic group, R ⁷ is a divalent organic group,
R ⁶ is

Embedded image (In the formula, R ⁸ is a monovalent organic group having any of an epoxy group, a carbon-carbon triple bond, or a carbon-carbon double bond.) A valent organic group, m is an integer of 1 or more, and n is an integer of 0 or more. In the eighth aspect of the present invention, a composition represented by the formula:
The Tg in the stage state is −20 ° C. to 150 ° C., and the Tg after curing is 70 ° C. to 300 ° C., and the soluble polyimide has a Tg of 100 ° C. to 300 ° C. and a thermal expansion coefficient after curing. A ninth aspect of the present invention relates to a coverlay film using the above composition, and a tenth aspect of the present invention relates to A.I. B. In addition to the components, C.I. The eleventh aspect of the present invention provides a photosensitive composition containing a photoreaction initiator or a sensitizer as an essential component.
A coverlay film using the photosensitive composition according to item 0,
The twelfth aspect of the present invention further relates to An epoxy resin having one or more epoxy rings in a molecule is prepared by using a plastic polyimide 10
A thirteenth aspect of the present invention relates to a photosensitive composition containing 1 to 100 parts by weight as an essential component with respect to 0 parts by weight.
A cover lay film using the photosensitive composition described in the above description.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition formed from at least a soluble polyimide and a compound having two or more carbon-carbon double bonds.

The term "soluble polyimide" used in the present invention includes commonly used organic solvents such as amides such as NMP, phenols such as cresol, ethers such as THF / dioxolan, and chlorine solvents such as methylene chloride. A polyimide that can be dissolved in any of solvents at room temperature in an amount of 1% by weight or more. Hereinafter, the contents of the present invention will be described in detail.

The soluble polyimide used in the composition of the present invention is obtained by mixing the above-mentioned acid dianhydride and the above-mentioned diamine in an organic solvent in a total molar amount of the acid dianhydride and a total molar amount of the diamine in substantially equimolar amounts. It is adjusted as such and reacted to produce polyamic acid, a precursor of polyimide. Thereafter, the polyamic acid is obtained by imidization.

The solubility of the polyimide of the present invention in an organic solvent depends on the structure of the polyimide. The acid dianhydride component and the diamine component can be selected within a range in which a structure capable of imparting solubility can be generated.However, it is possible to arbitrarily obtain various polyamic acid copolymers by adjusting these types and their molar ratios. Can be.

When a hydroxyl group and / or a carboxy group is introduced into the above-mentioned soluble polyimide, it can be reacted with a compound having a functional group such as an epoxy group. Therefore, it is possible to react with the below-mentioned component B or the like blended in the composition of the present invention.

The acid dianhydride used in the present invention is not particularly limited as long as it is an acid dianhydride. For example, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,2,
3,4-cyclobutanetetracarboxylic acid, 1,2,3
4-cyclopentanetetracarboxylic dianhydride, 2,
3,5-tricarboxycyclopentylacetic acid dianhydride,
3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl -3-cyclohexene-1,2-
Aliphatic or alicyclic tetracarboxylic dianhydrides such as dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′,
4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′ , 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride,
3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl Sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ',
4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene- Bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) ) Aromatic tetracarboxylic dianhydrides such as -4,4'-diphenylmethane dianhydride;
3,3a, 4,5,9b-Hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-
1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-
Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione;

[0014]

Embedded image

(In the formula, R9 represents a divalent organic group having an aromatic ring, and R10 and R11 each represent a hydrogen atom or an alkyl group.)

[0016]

Embedded image

Wherein R ¹² represents a divalent organic group having an aromatic ring, and R ¹³ and R ¹⁴ each represent a hydrogen atom or an alkyl group. Carboxylic dianhydrides and the like can be mentioned. These tetracarboxylic dianhydrides can be used alone or in combination of two or more. Among these, from the viewpoint of obtaining a soluble polyimide, one aromatic ring is used.
Acid dianhydrides having from 3 to 3 or alicyclic acid dianhydrides are preferred.

Further, Chemical formula 11

[0019]

Embedded image

(Wherein R ¹ is-, -CO-, -O-,
—C (CF ₃ ) ₂ — and —C (CH ₃ ) ₂ —, and R ² represents a divalent organic group. ) Is preferred. Particularly, in order to obtain a polyimide having high solubility in an organic solvent, 2,2′-hexafluoropropylidene diphthalic acid dianhydride is preferably used. Formula 12

[0021]

Embedded image

(Wherein R ¹⁵ represents a divalent organic group;

[0023]

Embedded image

(Wherein R ¹⁶ represents a hydrogen / halogen / methoxy / C1-C10 alkyl group). ) Represents a part of the ester dianhydride,
Preferably, it is desirable to use 10 to 100 mol% based on the total acid dianhydride.

The diamine used for the soluble polyimide may be a diamine having 1 to 6 aromatic rings or a diamine having a siloxane bond in an amount of 5 to 10 relative to the total diamine.
It is preferable to use 0 mol% to produce a soluble polyimide.

In particular,

[0027]

Embedded image

(Wherein R ³ represents —, —CO—, —O—,
—C (CF ₃ ) ₂ —, —C (CH ₃ ) ₂ —, —COO—
R ⁴ is hydrogen, halogen, a methoxy group, a C1 to C5 alkyl group, m is 0, 1, 2, 3 and n is 0, 1,
2, 3, and 4 are shown. ) Is preferably used in an amount of 10 to 100 mol% based on the total diamine.

The soluble polyimide which is a component of the composition of the present invention may have a hydroxyl group and / or a carboxy group introduced into a side chain. When a hydroxyl group and / or a carboxy group is introduced into the soluble polyimide, it can be reacted with a compound having a functional group such as an epoxy group. Therefore, the below-mentioned B compounded in the composition of the present invention
Reaction with components and the like is possible.

Here, for this purpose, hydroxyl groups and / or
Alternatively, a hydroxyl group and / or a carboxy group can be introduced into a soluble polyimide by reacting a diamine having a carboxy group with a suitable acid dianhydride.

As such a diamine, for example,
Diaminophenols such as 2,4-diaminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2 , 2'-dihydroxybiphenyl, 4,4'-diamino-2,2 ', 5
Hydroxybiphenyl compounds such as 5'-tetrahydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino-3,
3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane,
2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxyphenyl] hexa Fluoropropane, 4,4'-
Hydroxydiphenylalkanes such as hydroxydiphenylmethane such as diamino-2,2 ', 5,5'-tetrahydroxydiphenylmethane;3,3'-diamino-
4,4'-dihydroxydiphenyl ether, 4,4
'-Diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 4,4'-diamino-2,2',
Hydroxy diphenyl ether compounds such as 5,5'-tetrahydroxy diphenyl ether, 3,3'-diamino-4,4'-dihydroxy diphenyl sulfone,
4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 4,4'-diamino-2,2'-dihydroxydiphenylsulfone, 4,4'-diamino-
Diphenylsulfone compounds such as 2,2 ′, 5,5′-tetrahydroxydiphenylsulfone, 2,2-bis
Bis [(hydroxyphenyl) phenyl] alkane compounds such as [4- (4-amino-3-hydroxyphenoxy) phenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl; Bis (hydroxyphenoxy) biphenyl compounds, 2,2-bis
Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone; diaminobenzoic acids such as 3,5-diaminobenzoic acid; and 3,3′-diamino-4 ,
4'-dicarboxybiphenyl, 4,4'-diamino-
Carboxybiphenyl compounds such as 3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2'-dicarboxybiphenyl, 4,4'-diamino-2,2 ', 5,5'-tetracarboxybiphenyl , 3,3′-diamino-4,4′-dicarboxydiphenylmethane,
4,4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-
4-carboxyphenyl] propane, 2,2-bis [4-
Amino-3-carboxyphenyl] propane, 2,2-
Bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4'-diamino-2,2 ', 5
Carboxydiphenylalkanes such as carboxydiphenylmethane such as 5'-tetracarboxydiphenylmethane, 3,3'-diamino-4,4'-dicarboxydiphenylether, 4,4'-diamino-3,3'-dicarboxydiphenylether, , 4'-diamino-
2,2′-dicarboxydiphenyl ether, 4,4
Carboxydiphenyl ether compounds such as '-diamino-2,2', 5,5'-tetracarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenylsulfone, and 4,4'-diamino-3,3
Diphenylsulfone compounds such as '-dicarboxydiphenylsulfone, 4,4'-diamino-2,2'-dicarboxydiphenylsulfone, and 4,4'-diamino-2,2', 5,5'-tetracarboxydiphenylsulfone Bis [(carboxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, and 4,4'-bis (4-amino-3-hydrido) Bis (hydroxyphenoxy) biphenyl compounds such as xyphenoxy) biphenyl; 2,2-bis [4- (4-amino-3);
Bis [(carboxyphenoxy) phenyl] sulfone compounds such as -carboxyphenoxy) phenyl] sulfone;

The other diamine used in the production of the soluble polyimide is not particularly limited.
Phenylenediamine, m-phenylenediamine, 4,4
'-Diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4
'-Diaminodiphenylsulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl)
-1,3,3-trimethylindane, 6-amino-1-
(4'-aminophenyl) -1,3,3-trimethylindane, 4,4'-diaminobenzanilide, 3,5-
Diamino-3′-trifluoromethylbenzanilide,
3,5-diamino-4′-trifluoromethylbenzanilide, 3,4′-diaminodiphenyl ether, 2,
7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-
Tetrachloro-4,4'-diaminobiphenyl, 2,2
'-Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoro Methyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane,
2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 3'-bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene ) Bisaniline, 2,2′-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [4- (4-amino-2-trifluoromethyl) Phenoxy] -aromatic diamine such as octafluorobiphenyl; two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene Aromatic diamine having a hetero atom other than the nitrogen atom of the amino group; 1,1-methaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4 -Diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-
Aliphatic diamines and alicyclic diamines such as methanoindanylene dimethylene diamine, tricyclo [6,2,1,02.7] -undecylene dimethyl diamine, and 4,4′-methylene bis (cyclohexylamine);

[0033]

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Monosubstituted phenylenediamines represented by the formula (wherein R ¹⁷ is -O-, -COO-, -OCO-,-
CONH- and represents a divalent organic group selected from -CO-, R ¹⁸ is a monovalent organic group having a steroid skeleton. );

[0035]

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(R ¹⁹ is a hydrocarbon group having 1 to 12 carbon atoms, y is an integer of 1 to 3, and z is an integer of 1 to 20). . These diamine compounds can be used alone or in combination of two or more.

The organic polar solvent used in the polyamic acid formation reaction is not particularly limited as long as it can dissolve the polyamic acid. Synthesize polyamic acid,
Thereafter, the solvent is removed and the imidization is carried out simultaneously by reducing the pressure by heating, so that it is advantageous in terms of the process to dissolve the polyamic acid and select one having a boiling point as low as possible.

For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like. Acetamide solvent, N-methyl-2-pyrrolidone, N-vinyl-2
-A pyrrolidone solvent such as pyrrolidone, phenol, o
-, M- or p-cresol, xylenol, halogenated phenol, phenolic solvents such as catechol, ether solvents such as tetrahydrofuran, dioxane, dioxolane, alcoholic solvents such as methanol, ethanol, butanol, and cellosolves such as butyl cellosolve Alternatively, hexamethylphosphoramide, γ-butyrolactone and the like can be mentioned, and it is desirable to use these alone or as a mixture, but furthermore, aromatic hydrocarbons such as xylene and toluene can be used.

The method for producing the soluble polyimide will be specifically described below. Polyamic acid, which is a precursor of the soluble polyimide, is obtained by reacting the diamine with an acid dianhydride in an organic solvent. In an inert atmosphere such as argon or nitrogen, diamine is dissolved in an organic solvent or dispersed in a slurry state, and acid dianhydride is dissolved in an organic solvent and added in a slurry state or a solid state. I do.

As an addition method, for example, a diamine component-1 and a diamine component-2 may be added to an organic polar solvent first, and then an acid dianhydride component may be added to form a solution of a polyamic acid polymer. Alternatively, the diamine component-1 may be added first to the organic polar solvent, the acid dianhydride component may be added, and then the diamine component-2 may be added to form a polyamic acid polymer solution.

The diamine component-1 may be added first to the organic polar solvent, then the acid dianhydride component-1 may be added, and then the acid dianhydride-2 may be added to form a polyamic acid polymer solution.

Further, diamine component-1 and diamine component-
2 may be previously added to the organic polar solvent, acid dianhydride component-1 may be added, and then acid dianhydride-2 may be added to form a solution of a polyamic acid polymer.

The same is true even if the above addition method is reversed so that the acid dianhydride is added first and the diamine component is added later.

The reaction temperature at this time is preferably from -20 ° C to 90 ° C. The reaction time is about 30 minutes to 24 hours.

The polyamic acid has an average molecular weight of 5,000 to
Desirably, it is 1,000,000. When the average molecular weight is less than 5,000, the molecular weight of the completed polyimide composition also becomes low, and the resin tends to become brittle even when the polyimide composition is used as it is. On the other hand,
If it exceeds 000, the viscosity of the polyamic acid varnish becomes too high and handling becomes difficult, which is not preferable.

Next, the polyamic acid is imidized. In the present invention, a method of heating and drying the polyamic acid solution under reduced pressure to directly imidize the solution is used.

Here, water generated when the polyamic acid is imidized easily hydrolyzes the polyamic acid and causes a decrease in molecular weight. Conventionally, as a method of imidation while removing water, (1) a method of adding an azeotropic solvent such as toluene / xylene and removing the water by azeotropic distillation,
(2) There is a chemical imidation method in which an aliphatic dianhydride such as acetic anhydride and a tertiary amine such as triethylamine, pyridine, picoline and isoquinoline are added. However, in the removal of water by azeotropic distillation in (1), water is present in the solution system and hydrolysis by water cannot be avoided. In the chemical imidization method (2), the generated water is chemically removed by converting the aliphatic acid dianhydride into an aliphatic acid. Although advantageous, the aliphatic acid dianhydride / tertiary amine remains in the system, so that a step of removing these is required.

In the imidation method of the present invention, hydrolysis generated by heating and depressurizing water produced by the imidization and actively removing the water from the system can be suppressed, and a decrease in molecular weight can be avoided. In addition, when the acid dianhydride of the raw material used is mixed with, for example, a tetracarboxylic acid which has been ring-opened by hydrolysis or a substance in which one of the acid dianhydrides has been hydrolyzed, and the polymerization reaction of the polyamic acid is stopped. By decompression and heating during imidization, the ring-opened acid dianhydride is closed again to form an acid dianhydride, and reacts with the amine remaining in the system during imidization, and an improvement in molecular weight is expected. it can.

Hereinafter, the method of the present invention in which a polyamic acid solution is heated and dried under reduced pressure to directly imidize the polyamic acid solution will be described.

Basically, it is a method of drying by heating under reduced pressure. Specifically, in the case of a batch type, a vacuum oven is used, and in the case of a continuous type, for example, a 2-axis or 3-axis with a decompression device is attached. It can be performed by an extruder. These methods can be selected according to the production amount. In addition, the twin-screw or three-screw extruder with the decompression device referred to here is a general melt extruder that heat-melts and extrudes a thermoplastic resin, and is accompanied by a device that removes the solvent by decompressing a general melt extruder. It is.
The polyamic acid solution is kneaded by the extruder with a biaxial or triaxial extruder to remove the solvent and water generated at the time of imidization while kneading, thereby obtaining a desired soluble polyimide.

The heating conditions for imidization are from 80 ° C. to 400 ° C.
It is. The temperature is 100 ° C. or higher, preferably 120 ° C. or higher, at which imidization is efficiently performed and water is efficiently removed. The maximum temperature is desirably set to a temperature equal to or lower than the thermal decomposition temperature of the polyimide used. Usually, the imidization is almost completed at about 250 to 350 ° C.
It can be set to about 350 ° C.

The pressure is preferably reduced as long as the pressure under which the water generated during imidization is efficiently removed under the above heating conditions. Specifically, the pressure for heating under reduced pressure is 91,000 to 100 Pa, preferably 81,000 to 100 Pa, and more preferably 71,000 to 1000 Pa.

The soluble polyimide of the present invention can be compounded with various organic additives, inorganic fillers, or various reinforcing materials.

In the composition of the present invention, when the soluble polyimide is a soluble polyimide into which the above-mentioned hydroxyl group and / or carboxy group is introduced, a reactive group capable of reacting with the hydroxyl group and / or carboxy group, for example, an epoxy group is used. By reacting with a compound having the compound, it is possible to introduce another useful organic group. For example, a compound having an epoxy group and a carbon-carbon double bond in a molecule, a compound having an epoxy group having a carbon-carbon triple bond, two or more epoxy groups, acrylic acid or methacrylic acid, or one or more of these halides The modified polyimide can be produced by the reaction. These carbon-carbon double bonds,
By introducing a carbon-carbon triple bond or an epoxy group into the side chain of the soluble polyimide, the polyimide can be imparted with thermosetting properties, photosensitive properties, and the like.

That is, the soluble polyimide has the general formula (1)

[0056]

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(Where R ⁵ is a tetravalent organic group, R ⁷ is a divalent organic group, and R ⁶ is

[0058]

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(Wherein R ⁸ is a monovalent organic group having at least one selected from the group consisting of an epoxy group, a carbon-carbon triple bond, and a carbon-carbon double bond). A valent organic group containing 1 to 4 organic groups, m is an integer of 1 or more, and n is an integer of 0 or more. ) Is preferable.

Specifically, a soluble polyimide having a hydroxyl group and / or a carboxy group introduced therein is dissolved in an organic solvent,
An epoxy resin having two or more epoxy groups, or a compound having an epoxy group and a double bond or an epoxy group and a triple bond, or a mixture of acrylic acid, methacrylic acid, or a halide thereof to form a hydroxyl group or a carboxylic acid group of a soluble polyimide. A modified polyimide is obtained by reacting an acid group with an epoxy group.

The epoxy resin having two or more epoxy groups is not particularly limited as long as it has two or more epoxy groups in a molecule. Examples thereof include bisphenol resins such as Epicoat 828 (manufactured by Yuka Shell Co., Ltd.) and 180S65. Orthocresol novolak resin such as (manufactured by Yuka Shell Co.), 15
Bisphenol A novolak resin such as 7S70 (manufactured by Yuka Shell), trishydroxyphenylmethane novolak resin such as 1032H60 (manufactured by Yuka Shell), ESN
375, naphthalene aralkyl novolak resin, tetraphenylolethane 1031S (manufactured by Yuka Shell Co.),
YGD414S (manufactured by Toto Kasei), trishydroxyphenylmethane EPPN502H (manufactured by Nippon Kayaku), special bisphenol VG3101L (manufactured by Mitsui Chemicals), special naphthol NC7000 (manufactured by Nippon Kayaku), TETRAD-X,
Examples include glycidylamine type resins such as TETRAD-C (manufactured by Mitsubishi Gas Chemical Company) and alicyclic epoxy resins such as Adeka Optomer KRM-2110 (manufactured by Asahi Denka Kogyo KK).

The compound having an epoxy group and a carbon-carbon double bond is not particularly limited as long as it has an epoxy group and a carbon-carbon double bond in the molecule. For example, allyl glycidyl ether / glycidyl acrylate / Glycidyl methacrylate / glycidyl vinyl ether;

The compound having an epoxy group and a carbon-carbon triple bond is not particularly limited as long as the compound has an epoxy group and a carbon-carbon triple bond in the molecule. Examples thereof include propargyl glycidyl ether / glycidyl propiolate / ethynyl glycidyl ether. Is mentioned.

The solvent used in this reaction is not particularly limited as long as it does not react with the epoxy group and dissolves a soluble polyimide having a hydroxyl group or a carboxy group. After that, since the solvent is removed, it is advantageous in the production process to dissolve the soluble polyimide having a hydroxyl group or a carboxy group and to select the one having a boiling point as low as possible. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, N, N-dimethylacetamide
Acetamide solvents such as N-diethylacetamide,
Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; ether solvents such as tetrahydrofuran, dioxane and dioxolane; alcohol solvents such as methanol, ethanol and butanol; cellosolve solvents such as butyl cellosolve and Methyl phosphoramide, γ-butyrolactone, etc., and also aromatic hydrocarbons such as xylene and toluene can be used. These can be used alone or as a mixture.

The reaction is preferably carried out at a temperature of 40 ° C. or more and 130 ° C. or less, which is the reaction temperature between a hydroxyl group or a carboxy group and the above compound. In particular, compounds having an epoxy group and a double bond or a compound having an epoxy group and a triple bond are preferably reacted at a temperature at which the double bond or the triple bond is not decomposed or crosslinked by heat. Specifically, 40 degrees or more and 100 degrees or less, more desirably,
It is 50 degrees or more and 90 degrees or less. The reaction time is about several minutes to about eight hours.

As described above, the compound of the present invention is produced by mixing a compound having a carbon-carbon double bond with the obtained soluble polyimide solution.

The compound having a carbon-carbon double bond used in the present invention preferably has two or more carbon-carbon double bonds. This is because a compound having two or more carbon-carbon double bonds facilitates photopolymerization. Furthermore, a compound containing two or more organic groups selected from an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group is preferable.

Compounds having two or more carbon-carbon double bonds include, for example, 1,6-hexanediol diacrylate,
Neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexane Diol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,
Dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3- Chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate , Tri ethylene glycol di methacrylate, polyethylene glycol di methacrylate, 1,3-butylene glycol di methacrylate, 1,
6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3 dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy)
Phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4-
(Methacryloxy / polyethoxy) phenyl] propane,
Polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2-bis [4- (acryloxy.
Diethoxy) phenyl] propane, 2,2-bis [4-
(Acryloxypolyethoxy) phenyl] propane,
2-hydroxy 1-acryloxy 3-methacryloxy propane, trimethylol propane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3-methyl -1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate,
1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1,4
-Cyclohexane dimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4-
(Acryloxypolyethoxy) phenyl] propane,
2,2-bis [4- (acryloxypolypropoxy)
[Phenyl] propane, 2,4-diethyl-1,5-pentanediol diacrylate, ethoxylated tothymethylolpropane triacrylate, propoxylated tothymethylolpropane triacrylate, isocyanuric acid EO modified triacrylate, pentathritol tetraacrylate, ethoxylated Pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate, ditrimethylolpropanetetreacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloylhexahydro-s -Triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallylph Phosphate, 5,5-diallylbarbituric acid, diallylamine, diallyldimethylsilane, diallyl disulfide, diallyl ether, diallyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-diaryloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4
'-Isopropylidene diphenol dimethacrylate,
4,4′-isopropylidene diphenol diacrylate and the like are preferable, but not limited thereto. In order to improve the crosslink density, it is particularly desirable to use a bifunctional or higher functional monomer. In addition, one kind of compound may be used, or several kinds may be mixed and used.

The mixing ratio of these components is as follows.
1 to 150 parts by weight, and further 10 parts by weight
It is preferable that the content be in the range of from 130 to 130 parts by weight, particularly from 20 to 100 parts by weight. With this mixing ratio, the desired photosensitivity can be imparted to the polyimide.

The composition of the present invention comprising the above-mentioned compound having a soluble polyimide and a compound having a carbon-carbon double bond, has a Tg in the B-stage state of −20 ° C. to 150 ° C.
C, and Tg after curing is 70C to 300C, and the soluble polyimide has a Tg of 100C to 300C.
Having a thermal expansion coefficient of 20 ppm to 500 pp after curing.
m is preferable.

The composition solution of the present invention obtained above may optionally contain a thermosetting resin such as an epoxy resin or an acrylic resin,
Thermoplastic resins such as polyester, polyamide, polyurethane, and polycarbonate may be mixed.

The epoxy resin may be the same as the epoxy resin described above. For example, bisphenol resin such as Epicoat 828 (manufactured by Yuka Shell), ortho-cresol novolak resin such as 180S65 (manufactured by Yuka Shell),
Bisphenol A such as 157S70 (manufactured by Yuka Shell)
Novolak resin, trishydroxyphenylmethane novolak resin such as 1032H60 (manufactured by Yuka Shell), E
Naphthalene aralkyl novolak resin such as SN375,
Tetraphenylolethane 1031S (made by Yuka Shell), YGD414S (made by Toto Kasei), Trishydroxyphenylmethane EPPN502H (made by Nippon Kayaku), special bisphenol VG3101L (made by Mitsui Chemicals), special naphthol NC7000 (made by Nippon Kayaku) , TETRAD
-X, TETRAD-C (manufactured by Mitsubishi Gas Chemical Company) and other glycidylamine type resins, ADEKA OPTOMER KRM-211
0 (manufactured by Asahi Denka Kogyo KK) and the like. It is also preferable to mix with a thermosetting resin other than the epoxy resin because good physical properties can be obtained. The thermosetting resin used here is bismaleimide
Bisallylnadiimide, phenolic resin, cyanate resin and the like can be mentioned.

The obtained composition solution may be directly applied and dried, or may be separately processed into a sheet and then used by bonding the sheet to a portion to be joined. These drying conditions are desirably performed under such a condition that when an epoxy group, a double bond, or a triple bond is introduced into the soluble polyimide, the remaining organic groups are not decomposed or crosslinked by heat.

When a composition of the present invention containing an epoxy resin is mixed with a curing agent for an epoxy resin, a composition having good heat resistance and adhesive properties can be obtained. This is desirable because a cured product having characteristics can be obtained. If the curing agent is a curing agent for epoxy resin, amine-based, imidazole-based, acid anhydride-based,
Any acid-based curing agent is applicable, and various coupling agents may be mixed.

Next, a photoreaction initiator and / or a sensitizer is added to the modified polyamide to obtain a photosensitive composition of the present invention.

The photoreactive initiator is in the UV visible light range (25
(0-450 nm) and converts light energy into chemical energy that produces reactive intermediates such as free radicals and reactive cations. In particular, as an example of a compound that generates a radical by light having a long wavelength of about g-line,
The following general formula (α) and general formula (β)

[0077]

Embedded image

(Wherein R ²⁰ , R ²³ and R ²⁵ are C ₆ H
_{5 -, C 6 H 4 (} CH 3) -, C 6 H 2 (CH 3) 3 -, (CH
_{3) 3 C-, C 6 H} 3 Cl 2 - a, R ^21, R ²² and R ²⁴ are,
C ₆ H ₅ -, methoxy, _{ethoxy, C 6 H 4 (CH 3} ) -,
Represents C ₆ H ₂ (CH ₃ ) ₃ —. )). The radicals generated thereby react with a reactive group having a carbon-carbon double bond (vinyl, acryloyl, methacryloyl, allyl, etc.) to promote crosslinking.

Here, the general formula (α) generates two radicals, and the acylphosphine oxide represented by the general formula (β) is particularly preferable because it generates four radicals by α-cleavage. .

In order to cure the epoxy group bonded to the side chain of the soluble polyimide in the photosensitive composition of the present invention, a photo cation generator may be used. For example, diphenyliodonium salts such as diphenyliodonium salt of dimethoxyanthraquinonesulfonic acid, triphenylsulfonium salts, pyrilinium salts, triphenylonium salts, diazonium salts and the like can be exemplified.

When a photocationic generator is used, it is preferable to mix an alicyclic epoxy or vinyl ether compound having high cationic curability.

In order to cure the epoxy group attached to the side chain, a photobase generator may be used. For example, urethane compounds obtained by the reaction of nitrobenzyl alcohol or dinitrobenzyl alcohol with isocyanate, urethane compounds obtained by the reaction of nitro-1-phenylethyl alcohol or dinitro-1-phenylethyl alcohol with isocyanate, dimethoxy-2 Examples thereof include urethane compounds obtained by the reaction of -phenyl-2-propanol and isocyanate.

As the radical initiator, various peroxides can be used in combination with the following sensitizers. Particularly preferred is a combination of 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and a sensitizer.

The photosensitive composition used in the present invention preferably contains a sensitizer in order to achieve a practically usable photosensitive sensitivity. Preferred examples of the sensitizer include Michler's ketone, bis-4,4'-diethylaminobenzophenone,
Benzophenone, camphorquinone, benzyl, 4,
4'-dimethylaminobenzyl, 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-bis (dimethylaminobenzylidene) -N
-Methyl-4-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone,
3,3'-carbonylbis (7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-dimethylthioxanthone,
2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2- (ethoxycarbonyl) oxyiminopropan-1-one, benzoin ether, benzoin Isopropyl ether, benzanthrone, 5-nitroacenaphthene, 2-nitrofluorene, anthrone, 1,2-
Benzanthraquinone, 1-phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one,
0-thioxanthenone, 3-acetylindole, 2,
6-di (p-dimethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6
-Di (p-diethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4-hydroxycyclohexanone, 4,6-
Dimethyl-7-ethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 7-diethylamino-3-
(1-methylbenzimidazolyl) coumarin, 3- (2
-Benzimidazolyl) -7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl)
Quinoline, 4- (p-dimethylaminostyryl) quinoline, 2- (p-dimethylaminostyryl) zenzothiazole, 2- (p-dimethylaminostyryl) -3,3-
Examples include, but are not limited to, dimethyl-3H-indole.

The photopolymerization initiator and / or sensitizer is used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyimide resin of the present invention.
It is preferable to mix the parts by weight, more preferably 0.3 to 20 parts by weight. If the amount is out of the range of 0.1 to 50 parts by weight, the sensitizing effect may not be obtained or the developability may be unfavorably affected. As the sensitizer, one compound may be used, or several compounds may be used as a mixture.

The photosensitive polyimide composition used in the present invention is intended to achieve a practically usable photosensitive sensitivity.
It is desirable to include a photopolymerization aid. As the photopolymerization auxiliary, for example, 4-diethylaminoethyl benzoate, 4
-Dimethylaminoethyl benzoate, 4-diethylaminopropyl benzoate, 4-dimethylaminopropyl benzoate, 4-dimethylaminoisoamyl benzoate, N-phenylglycine, N-methyl-N-phenylglycine, N- (4-cyanophenyl) glycine, 4−
Dimethylaminobenzonitrile, ethylene glycol dithioglycolate, ethylene glycol di (3-mercaptopropionate), trimethylolpropanethioglycolate, trimethylolpropanetri (3-mercaptopropionate), pentaerythritol tetrathioglycolate Pentaerythritol tetra (3-mercaptopropionate), trimethylolethanetrithioglycolate, trimethylolpropanetrithioglycolate, trimethylolethanetri (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate) Propionate), thioglycolic acid, α-mercaptopropionic acid, t-butylperoxybenzoate, t-butylperoxymethoxybenzoate, t-butylperoxide Shi nitrobenzoate, t
-Butyl peroxyethyl benzoate, phenyl isopropyl peroxy benzoate, di-t-butyl diperoxy isophthalate, tri-t-butyl triperoxy trimellitate, tri-t-butyl triperoxy trimellitate, tetra-t-butyl tetraperoxy pyromellitate, 2 , 5-Dimethyl-2,5-di (benzoylperoxy) hexane, 3,3 ′, 4,4′-tetra (t
-Butylperoxycarbonyl) benzophenone, 3,
3,4,4'-tetra (t-amylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t
-Hexylperoxycarbonyl) benzophenone,
2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (p-azidobenzal) -4-
Carboxycyclohexanone, 2,6-di (p-azidobenzal) -4-methoxycyclohexanone, 2,6-
Di (p-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (p-azidobenzal) -1
-Methyl-4-piperidone, 3,5-di (p-azidobenzal) -4-piperidone, 3,5-di (p-azibenzal) -N-acetyl-4-piperidone, 3,5-di (p-
Azidobenzal) -N-methoxycarbonyl-4-piperidone, 2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (m-azidobenzal) -4-carboxycyclohexanone, 2,6-di ( m
-Azidobenzal) -4-methoxycyclohexanone,
2,6-di (m-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (m-azidobenzal) -N-methyl-4-piperidone, 3,5-di (m-azidobenzal) -4 -Piperidone, 3,5-di (m-azidobenzal) -N-acetyl-4-piperidone, 3,5-
Di (m-azidobenzal) -N-methoxycarbonyl-4
-Piperidone, 2,6-di (p-azidocinnamylidene) -4-hydroxycyclohexanone, 2,6-di (p
-Azidocinnamylidene) -4-carboxycyclohexanone, 2,6-di (p-azidocinnamylidene) -4-
Cyclohexanone, 3,5-di (p-azidocinnamylidene) -N-methyl-4-piperidone, 4,4′-diazidochalcone, 3,3′diazidochalcone, 3,4′-
Diazido chalcone, 4,3′-diazido chalcone, 1,
3-diphenyl-1,2,3-propanetrione-2-
(O-acetyl) oxime, 1,3-diphenyl-1,
2,3-propanetrione-2- (on-propylcarbonyl) oxime, 1,3-diphenyl-1,2,3
-Propanetrione-2- (o-methoxycarbonyl)
Oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxime,
1,3-diphenyl-1,2,3-propanetrione-
2- (o-benzoyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-phenyloxycarbonyl) oxime, 1,3-bis (p-methylphenyl) -1,2 , 3-propanetrione-2- (o
-Benzoyl) oxime, 1,3-bis (p-methoxyphenyl) -1,2,3-propanetrione-2- (o-
Ethoxycarbonyl) oxime, 1- (p-methoxyphenyl) -3- (p-nitrophenyl) -1,2,3-
Although propanetrione-2- (o-phenyloxycarbonyl) oxime and the like can be used, the present invention is not limited thereto. Also, as another auxiliary agent, triethylamine
Trialkylamines such as tributylamine and triethanolamine can also be mixed.

The photopolymerization aid is preferably blended in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polyimide.
The range is more preferably from 0.3 to 20 parts by weight. 0.1 ~
If the content is outside the range of 50 parts by weight, the intended sensitizing effect may not be obtained, or the developing property may be adversely affected. In addition, one kind of compound may be used as the photopolymerization aid, or several kinds may be mixed.

The photosensitive polyimide used in the present invention is:
It may contain a suitable organic solvent. If it is dissolved in an appropriate organic solvent, it can be used in a solution (varnish) state, which is convenient when forming a film. As the solvent used in this case, an aprotic polar solvent is desirable from the viewpoint of solubility.Specifically, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, dioxane, Preferred examples include dioxolan and tetrahydrofuran. These may be used alone or as a mixed system. This organic solvent may be a solvent in which the solvent used in the synthesis reaction of the polyimide is left as it is, or may be a newly added solvent to the isolated polyimide precursor. Further, in order to improve coatability, a solvent such as toluene, xylene, diethyl ketone, methoxybenzene, or cyclopentanone may be mixed within a range that does not adversely affect the solubility of the polymer.

The obtained solution of the photosensitive polyimide composition is dried to obtain a film-shaped photosensitive dry film (coverlay film). At this time, it may be applied on a support such as a film of metal or PET, dried and dried, and then peeled off from the support and handled as a single film.
It can be used as it is laminated on a film such as PET. The drying temperature of the photosensitive polyimide composition is preferably set to a temperature at which epoxy or a carbon-carbon double bond or a carbon-carbon triple bond is not thermally decomposed or crosslinked by heat, and specifically 180 ° C. or less. Is 150 ° C. or less.

The step of laminating the photosensitive dry film (coverlay film) thus obtained and the FPC will be described. This step is a step of protecting the conductor surface of the FPC on which a circuit is formed in advance by a conductor such as a copper foil with a photosensitive dry film (coverlay film). Specifically, the FPC and the photosensitive dry film (coverlay film) are bonded together by heat lamination, hot press or hot vacuum lamination.
The temperature at this time is desirably set at a temperature at which the epoxy or carbon-carbon double bond or carbon-carbon triple bond is not thermally decomposed or crosslinked by heat, and specifically, 180 ° C or lower, preferably 150 ° C or lower. , More preferably 120
It is below ° C.

The lamination temperature is closely related to the Tg of the B-stage state of the coverlay film, and
For laminating or pressing at a temperature of 80 ° C. or less, it is 150 ° C. or less, preferably 130 ° C. or less, more preferably 100 ° C. or less, and most preferably 50 ° C. or less.
It is as follows.

Next, after irradiating the film with light through a photomask having a predetermined pattern, an unexposed portion is dissolved and removed with a basic solution to obtain a desired pattern. This developing step may be performed using a general positive type photoresist current developing device.

As the developing solution, a basic solution or an organic solvent can be used. For example, the developer may be a solution of one type of compound or a solution of two or more types of compounds as long as it is an aqueous solution or an organic solvent exhibiting basicity. The basic solution is usually a solution in which a basic compound is dissolved in water or an alcohol such as methanol. The concentration of the basic compound is usually 0.1 to 50% by weight.
It is preferable that In order to improve the solubility of polyimide, water-soluble organic liquids such as methanol, ethanol, propanol, isopropyl alcohol, N-methyl-2-pyrrolidone N, N-dimethylformamide, N, N-dimethylacetamide, etc. A cleaning medium may be further contained.

Examples of the basic compound include borates and carbonates of alkali metals, alkaline earth metals and ammonium ions, amine compounds, and the like. Specific examples include 2-dimethylaminoethanol, 3−
Dimethylamino-1-propanol, 4-dimethylamino-1-butanol, 5-dimethylamino-1-pentanol, 6-dimethylamino-1-hexanol, 2-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, Nt-butyldiethanolamine,
N-lauryldiethanolamine, 3-diethylamino-
1,2-propanediol, triethanolamine, triisopropanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-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 hydrogen carbonate, Potassium bicarbonate, ammonium bicarbonate,
Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, aminomethanol, 2-aminoethanol, 3
-Aminopropanol, 2-aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine,
It is preferable to use triethylamine, tripropylamine, triisopropylamine and the like, but other compounds may be used as long as they are soluble in water or alcohol and the solution exhibits basicity.

In addition to the basic solution, the developing solution
Organic solvents can be used. In this case, the organic solvent may be used alone, or a mixed system of a good solvent that dissolves the photosensitive polyimide well and a poor solvent that does not dissolve the photosensitive polyimide may be used.

The 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 pattern bound by the above processing is
By performing the heat treatment at a selected temperature from 20 ° C. to 200 ° C., the polyimide resin pattern of the present invention is bound with high resolution. This resin pattern has high heat resistance and excellent mechanical properties.

The higher the Tg after curing is, the higher the heat resistance is. However, in practice, it is 70 to 300 ° C., preferably 90 to 300 ° C., and more preferably 120 to 300 ° C. is there.

The thermal expansion coefficient of the coverlay film is preferably slightly larger than the thermal expansion coefficient of the copper foil.
00 ppm, more preferably 20 to 400 ppm
, Most preferably from 20 to 300 ppm.

[0100]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

In the examples, ESDA was 2,2-bis (4
-Hydroxyphenyl) propanedibenzoate-3,
3 ', 4,4'-tetracarboxylic dianhydride, 6FDA
Is 2,2'-hexafluoropropylidene diphthalic dianhydride, BAPS-M is bis [4- (3-aminophenoxy) phenyl] sulfone, DMAc is N, N
-Dimethylacetamide, DMF represents N, N-dimethylformamide.

Tg: DSC CELL, Shimadzu Corporation
The temperature range from room temperature to 400 ° C. was measured with a SCC-41 (differential scanning calorimeter) at a heating rate of 10 ° C./min under a nitrogen stream.

The weight average molecular weight was measured by GPC manufactured by Waters.
Was measured under the following conditions. (Column: Shodex
KD-806M two, temperature 60 ° C, detector: R
I, flow rate: 1 ml / min, developing solution: DMF (lithium bromide 0.03 M, phosphoric acid 0.03 M), sample concentration: 0.2 w
t%, injection volume: 20 μl, reference substance: polyethylene oxide)

The imidation ratio was measured as follows. : Polyamic acid solution (DMF solution) was cast on a PET film, heated at 100 ° C. for 10 minutes and 130 ° C. for 10 minutes, peeled off the PET film, and fixed on a pin frame.
Heat at 150 ° C. for 60 minutes, 200 ° C. for 60 minutes and 250 ° C. for 60 minutes to obtain a 5 μm thick polyimide film. Dissolve the polyimide prepared in Examples or Comparative Examples in DMF,
After being cast on a PET film, heated at 100 ° C. for 30 minutes, peeled off from the PET film, fixed to a pin frame, and heated and dried in a vacuum oven at 80 ° C. and 660 Pa for 12 hours to obtain a 5 μm thick polyimide film. Was. The IR of each film is measured, and the ratio of imide absorption / benzene ring absorption is determined. Assuming that the ratio of the imide absorption / benzene ring obtained in the above is 100%, the ratio of the imide absorption / benzene ring corresponds to%. This was taken as the imidation ratio.

The coefficient of thermal expansion was measured with a thermal analyzer TMA-120C manufactured by Seiko Electronic Industry Co., Ltd.
The average thermal expansion coefficient at 00 ° C. was defined as the thermal expansion coefficient after curing.
The adhesive strength was measured according to JIS-C-5016.

[0106]

Example 1 (Synthesis of soluble polyimide) BAPS- was placed in a 2000 ml separable flask equipped with a stirrer.
43.05 g (0.1 mol) of M and 300 g of DMF were taken, and 57.65 g (0.10 mol) of ESDA were added at once with vigorous stirring, and stirring was continued for 30 minutes to obtain a polyamic acid solution. The weight average molecular weight (hereinafter referred to as Mw) of this polyamic acid was 62,000.

The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and placed in a vacuum oven for 15 minutes.
0 ° C 10 minutes, 160 ° C 10 minutes, 170 ° C 10 minutes, 180
10 minutes at 190 ° C, 30 minutes at 210 ° C, 660 Pa
Heated under reduced pressure.

It was taken out from the vacuum oven to obtain 96 g of a thermoplastic polyimide. The Mw of this polyimide is 6.8
The Tg was 200 ° C. and the imidation ratio was 100%.

(Production of a photosensitive composition and a coverlay film comprising the same) The above-obtained soluble polyimide 30
g, 70 g of dioxolane, 0.5 g of 4,4′-diaminodiphenylsulfone (hereinafter abbreviated as DDS), 0.5 g (1.2 mmol) of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 30 g of isocyanuric acid EO-modified triacrylate, bisphenol A type epoxy resin (manufactured by Yuka Shell Co., Ltd .: Epicoat 8)
28) The solution to which 3 g was added was applied on a PET film, dried at 45 ° C. for 5 minutes, the PET film was peeled off, fixed with a pin frame, dried at 65 ° C. for 5 minutes and at 80 ° C. for 30 minutes to obtain a photosensitive composition. Of a coverlay film having a thickness of 35 μm.

(Production of CCL) Polyimide film 25
The adhesive surface of Hilux LF0100 made by DuPont was superimposed on NPI (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) and laminated at 180 ° C. Peel off the release paper of Hilux, layer 1 ounce of copper foil 3ECVLP (Mitsui Metals)
Lamination was performed at 80 ° C., and heating was performed at 180 ° C. for 1 hour, a pattern was formed by etching, and CCL was obtained. This CCL
And the coverlay film obtained above and a Teflon sheet (release paper) having a thickness of 50 μm are stacked on each other at 120 ° C. and 1 N /
It was laminated under the condition of cm. After laminating and exposing for 3 minutes (exposure conditions: 400 nm light at 10 mJ / c)
m ² ), post-baking at 100 ° C. for 3 minutes, development with a 1% methanol solution of tetramethylammonium hydroxide (solution temperature 40 ° C.), 100 ° C. for 2 hours, 120 ° C. for 2 hours, 140 ° C. for 2 hours, 160 ° C. for 3 hours Cured under time conditions.

Separately, a copper foil / the above-obtained coverlay film / a 50 μm-thick Teflon sheet (release paper) is laminated, laminated, exposed, developed and cured under the same conditions as above, and the adhesive strength and the thermal expansion coefficient are determined. Was measured. The bond strength between the coverlay film and the copper foil after curing is 1.5 N
/ Cm, and a pattern of 100 μm line / space could be formed. The copper foil was removed by etching, and the remaining cured coverlay film was immersed in an NMP solution heated to 50 ° C. for 10 minutes, but did not dissolve at all.

The thermal expansion coefficient of the cured coverlay film was 55 ppm from room temperature to 100 ° C.

[0113]

Example 2 (Synthesis of soluble polyimide) BAPS-M was placed in a 2000 ml separable flask equipped with a stirrer.
Take 43.05 g (0.1 mol) and 300 g of DMF,
115.3 g (0.20 mol) of ESDA was added at once with vigorous stirring, and stirring was continued for 30 minutes. Then, 15.2 g (0.1 mol) of diaminobenzoic acid was added to D
It was dissolved in 150 g of MF, added to the above solution, and stirred for 30 minutes to obtain a polyamic acid solution. The weight average molecular weight (hereinafter, referred to as Mw) of this polyamic acid was 60,000.

This polyamic acid solution is placed on a Teflon-coated vat, and placed in a vacuum oven at 150 ° C. for 10 minutes.
160 ° C for 10 minutes, 170 ° C for 10 minutes, 180 ° C for 10 minutes, 1
The mixture was heated under reduced pressure at 660 Pa at 90 ° C. for 10 minutes and 210 ° C. for 30 minutes.

The resin was taken out of the vacuum oven to obtain 160 g of a soluble thermoplastic polyimide having a carboxylic acid.
The Mw of the polyimide was 65,000, the Tg was 190 ° C., and the imidation ratio was 100%.

(Synthesis of Modified Polyimide) 33 g of the soluble thermoplastic polyimide thus synthesized was dissolved in 66 g of dioxolan, and 2.85 g (25 mmol) of allyl glycidyl ether was dissolved in 25 g of dioxolan and added. 70 ° C
For 2 hours to synthesize a modified polyimide.

(Production of a photosensitive composition and a coverlay film comprising the same)
0 g, 0.5 g of 4,4'-diaminodiphenylsulfone (hereinafter abbreviated as DDS), 0.5 g (1.2 mmol) of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, isocyanuric acid 30 g of EO-modified triacrylate, 3 g of bisphenol A type epoxy resin Epicoat 828 (trade name: Yuka Shell Co., Ltd.)
Is applied on a PET film, and the solution is added at 45 ° C.
After drying, the PET film was peeled off, fixed with a pin frame, and dried at 65 ° C. for 5 minutes and at 80 ° C. for 30 minutes to obtain a 35 μm-thick coverlay film made of the photosensitive composition.

(Production of CCL) Polyimide film 25
The adhesive surface of Hilux LF0100 made by DuPont was superimposed on NPI (manufactured by Kanegafuchi Chemical Industry Co., Ltd.) and laminated at 180 ° C. Peel off the release paper of Hilux, layer 1 ounce of copper foil 3ECVLP (Mitsui Metals)
Lamination was performed at 80 ° C., and heating was performed at 180 ° C. for 1 hour, a pattern was formed by etching, and CCL was obtained. This CCL
And the coverlay film obtained above and a Teflon sheet (release paper) having a thickness of 50 μm are stacked on each other at 120 ° C. and 1 N /
It was laminated under the condition of cm. After laminating and exposing for 3 minutes (exposure conditions: 400 nm light at 10 mJ / c)
m ² ), post-baking at 100 ° C. for 3 minutes, development with a 1% methanol solution of tetramethylammonium hydroxide (solution temperature 40 ° C.), 100 ° C. for 2 hours, 120 ° C. for 2 hours, 140 ° C. for 2 hours, 160 ° C. for 3 hours Cured under time conditions.

Separately, a copper foil / the above-obtained coverlay film / a 50 μm-thick Teflon sheet (release paper) are laminated, laminated, exposed, developed and cured under the same conditions as described above to obtain an adhesive strength and a thermal expansion coefficient. Was measured. The bond strength between the coverlay film and the copper foil after curing is 1.5 N
/ Cm, and a pattern of 100 μm line / space could be formed. The copper foil was removed by etching, and the remaining cured coverlay film was immersed in an NMP solution heated to 50 ° C. for 10 minutes, but did not dissolve at all.

The thermal expansion coefficient of the cured coverlay film was 65 ppm from room temperature to 100 ° C.

[0121]

Example 3 (Synthesis of modified polyimide) Soluble thermoplastic polyimide 3 having a carboxy group synthesized in Example 2
3 g was dissolved in 66 g of dioxolane, and 1.4 g (12 mmol) of glycidyl methacrylate was dissolved in 10 g of dioxolane and added thereto. After heating and stirring at 60 ° C. for 30 minutes, the alicyclic epoxy resin ADEKA OPTOMER KRM-21 was added.
After adding 3.4 g (12 mmol) of 10 (trade name: manufactured by Asahi Denka Kogyo), the mixture was heated and stirred at 60 ° C. for 60 minutes to synthesize a modified polyimide.

(Production of Photosensitive Composition, Coverlay Film Consisting of It, CCL) 0.5 g of 4,4′-diaminodiphenylsulfone (hereinafter abbreviated as DDS) and bis (2, 4,6-
A solution containing 0.5 g (1.2 mmol) of trimethylbenzoyl) -phenylphosphine oxide and 30 g of isocyanuric acid EO-modified triacrylate was formed into a film under the same conditions as in Example 1 to produce a CCL.

The adhesive strength between the coverlay film and the copper foil is as follows:
It was 1.4 N / cm, and a 100 μm line / space pattern could be formed. The copper foil of the copper-clad plate was removed by etching, and the remaining cured coverlay film was immersed in an NMP solution heated to 50 ° C. for 10 minutes, but did not dissolve at all.

The thermal expansion coefficient of the cured cover lay film was 48 ppm from room temperature to 100 ° C.

[0125]

Example 4 Modified polyimide solution 1 synthesized in Example 2
To 00 g, 3 g of ADEKA OPTOMER KRM-2110 (trade name: manufactured by Asahi Denka Kogyo) 0.6 g of 4′-bis (diethylamino) benzophenone, 1.0 g of benzyl, 0.6 g of tributylamine, EO-modified isocyanuric acid triacrylate NK Example 1 A solution containing 30 g of an ester (trade name: Shin-Nakamura Chemical Co., Ltd.) and 0.5 g of DDS was added.
A film was formed under the same conditions as in Example 1 to prepare a CCL and copper-clad board.

The adhesive strength between the coverlay film and the copper foil is as follows:
It was 1.7 N / cm, and a 100 μm line / space pattern could be formed. The copper foil of the copper-clad plate was removed by etching, and the remaining cured coverlay film was immersed in an NMP solution heated to 50 ° C. for 10 minutes, but did not dissolve at all.

The thermal expansion coefficient of the cured coverlay film was 49 ppm at room temperature to 200 ° C., and 200 to 300 ppm.
It was 79 ppm at ° C.

[0128]

Example 5 (Synthesis of soluble polyimide) BAPS-M was placed in a 2000 ml separable flask equipped with a stirrer.
68.88 g (0.16 mol) and 300 g of DMF were taken, and 115.3 g (0.20 mol) of ESDA was added at once with vigorous stirring, and stirring was continued for 30 minutes. Next, 4.32 g (0.02 mol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl was added,
The mixture was stirred for 30 minutes, and then the above formula 16 (y = 3, R
¹² = methyl group, z = 13 (average)), silicon diamine 66M13 (trade name: PCR Inc.
26g (0.02 mol) was added and stirred for 30 minutes to obtain a polyamic acid solution. Mw of this polyamic acid
Was 58,000. The reaction was performed while cooling with ice water.

This polyamic acid solution is placed on a Teflon-coated vat and placed in a vacuum oven at 150 ° C. for 10 minutes.
160 ° C for 10 minutes, 170 ° C for 10 minutes, 180 ° C for 10 minutes, 1
The mixture was heated under reduced pressure at 660 Pa at 90 ° C. for 10 minutes and 210 ° C. for 30 minutes.

The product was taken out of the vacuum oven to obtain 202 g of a soluble thermoplastic polyimide having a hydroxyl group. The Mw of this polyimide was 62,000, the Tg was 190 ° C., and the imidation ratio was 100%.

(Synthesis of Modified Polyimide) 33 g of the synthesized soluble thermoplastic polyimide was dissolved in 66 g of dioxolane, and 0.5 g of triethylamine and 1.0 g (7 mmol) of glycidyl methacrylate were added thereto.
Dissolved in 5 g and added. Heating and stirring were performed at 60 ° C. for 2 hours to synthesize a modified polyimide.

(Production of photosensitive composition, cover lay film and CCL) DD was added to 100 g of the modified polyimide solution.
S 0.5 g, 3,3′-carbonylbis [7- (diethylamino) coumarin] 0.3 g, benzophenone 1 g,
A solution to which 0.5 g of tributylamine, 30 g of isocyanuric acid EO-modified triacrylate, and 3 g of bisphenol A type epoxy resin Epicoat 828 (trade name: manufactured by Yuka Shell Co., Ltd.) was applied on a pet film. Thus, a cover lay film having a thickness of 35 μm comprising the photosensitive composition was obtained. Further, in the same manner as in Example 1, C
CL and a copper-clad board were obtained.

The adhesive strength between the coverlay film and the copper foil is as follows:
It was 1.7 N / cm, and a 100 μm line / space pattern could be formed. The copper foil of the copper-clad plate was removed by etching, and the remaining cured coverlay film was immersed in an NMP solution heated to 50 ° C. for 10 minutes, but did not dissolve at all.

The thermal expansion coefficient of the cured coverlay film was 60 ppm from room temperature to 100 ° C.

[0135]

As described above, the present invention is a composition containing at least a soluble polyimide and a compound having two or more carbon-carbon double bonds as essential components, and is useful as a photosensitive composition. In addition, this composition has a Tg in a B stage state of −20 ° C. to 150 ° C. and a Tg after curing of 70 ° C. to 3 °
00 ° C. and the soluble polyimide has a Tg of 10
0 ° C to 300 ° C and the thermal expansion coefficient after curing is 20ppm
~ 500 ppm of the composition, and further to this composition,
An epoxy resin, and / or a photosensitive polyimide composition to which a photoreaction initiator or a sensitizer is added as an essential component,
It is particularly useful as a photosensitive composition. A coverlay film using these photosensitive polyimide compositions has sufficient mechanical strength, excellent heat resistance, and excellent workability and adhesiveness, particularly excellent low moisture absorption.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 79/08 C08L 79/08 Z 5E314 G03F 7/004 512 G03F 7/004 512 7/027 502 7/027 502 7/037 501 7/037 501 501 7/038 504 7/038 504 H05K 3/28 H05K 3/28 DF term (reference) 2H025 AA10 AA14 AB11 AC01 AD01 BC13 BC42 BC69 BJ09 CB25 CB30 CB41 4F071 AA42 AA51 AA60 AC03 AC10 AC12 AC13 AC15 AC16 AC19 AE06 AH04 AH13 BC01 4J002 CD00X CD02X CD05X CD06X CD07X CD13X CH05Y CM04W EB007 ED026 EE037 EH046 EH076 EH106 EH146 EL026 EL036 EL097 EN026 EN077 EV017 EV007 EG007 EB007 GQ05 4J011 AA05 PA97 PB39 QA03 QA08 QA12 QA13 QA20 QA22 QA23 QA24 QA26 QA27 QA39 QA 40 QB16 SA21 SA31 SA41 SA62 SA63 SA64 SA78 SA82 SA83 SA84 SA87 UA01 WA02 4J026 AB34 AB36 AC23 BA16 BA19 BA22 BA27 BA28 BA29 BA30 BA39 BA40 BA41 BA43 BA50 CA02 CA03 DB36 GA07 GA08 5E314 AA27 AA36 CC15 DD07 FF06 GG01 GG08

Claims (13)

[Claims] 1. A composition comprising, as essential components, at least a soluble polyimide and a compound having two or more carbon-carbon double bonds. 2. At least A. Soluble polyimide: 1
00 parts by weight, B.I. Acryloyl group, methacryloyl group,
A compound containing two or more organic groups selected from the group consisting of a vinyl group and an allyl group: a composition containing 1 to 150 parts by weight as an essential component. 3. The soluble polyimide has an aromatic ring of 1 to 3.
The composition according to claim 1, wherein the composition is obtained by using an acid dianhydride having three or an alicyclic acid dianhydride. 4. The method according to claim 1, wherein the soluble polyimide has one or more aromatic rings.
The composition according to any one of claims 1 to 3, wherein the composition is obtained by using a diamine having six or a diamine having a siloxane bond in an amount of 5 to 100 mol% based on all diamines. 5. The method according to claim 1, wherein the soluble polyimide is (Wherein, R ¹ represents —, —CO—, —O—, —C (CF ₃ )
_{2 -, - C (CH 3} ) 2 - a, R ² represents a divalent organic group. The composition according to claim 3 or 4, wherein the composition is obtained by using an acid dianhydride selected from the group consisting of 10 to 100 mol% based on the total acid dianhydride. 6. The soluble polyimide according to claim 2, wherein (Wherein, R ³ is —, —CO—, —O—, —C (CF ₃ )
_{2 -, - C (CH 3} ) 2 -, - COO- a, R ⁴ is hydrogen,
A halogen, a methoxy group, a C1-C5 alkyl group
Represents 0, 1, 2, 3 and n represents 0, 1, 2, 3, 4. ) Is selected from 10 to 10
6. The composition of claim 4, which is obtained by using 100 mol%.
A composition as described. 7. The method according to claim 1, wherein the soluble polyimide has a general formula (1)
Chemical formula 3 Chemical formula 3 (Where R ⁵ is a tetravalent organic group, R ⁷ is a divalent organic group,
R ⁶ is Chemical Formula 4 (Wherein R ⁸ is a monovalent organic group having at least one selected from the group consisting of an epoxy group, a carbon-carbon triple bond, or a carbon-carbon double bond).
A valent organic group containing an organic group of 4, m is an integer of 1 or more, and n is an integer of 0 or more. The composition according to any one of claims 1 to 6, which is represented by: 8. The composition according to claim 1, wherein the Bg stage has a Tg of −20 ° C. to 150 ° C., and a cured Tg of 70 ° C. to 3 ° C.
00 ° C., and the soluble polyimide has a Tg of 100 ° C. to 300 ° C. and a thermal expansion coefficient of 20 after curing.
The composition according to any one of claims 1 to 7, wherein the composition is from ppm to 500 ppm. 9. A coverlay film using the composition according to claim 1 or 2. 10. A. B. In addition to the components, C.I. 3. The photosensitive composition according to claim 1, comprising a photoreaction initiator and / or a sensitizer as an essential component. 11. A coverlay film using the photosensitive composition according to claim 10. 12. The method according to claim 12, wherein An epoxy resin having one or more epoxy rings in a molecule is prepared by using soluble polyimide 100
The photosensitive composition according to claim 9, wherein 1 to 100 parts by weight is an essential component with respect to parts by weight. 13. A coverlay film using the photosensitive composition according to claim 12.