KR20100125467A - Polyimide precursor, photosensitive polyimide precursor composition, photosensitive dry film, and flexible printed circuit board using those materials - Google Patents

Abstract

(X 는 탄소수가 3 내지 30 인 알킬렌기를 갖는 2 가의 유기기이다. R₁ 은 수소 원자, 탄소수가 1 내지 10 인 1 가의 알킬기, 알콕시기, 또는 할로겐기를 나타낸다) The photosensitive dry film has no tackiness, there is no crack in the photosensitive layer even when the photosensitive dry film is bent after the desolvent, lithography is good, and when used for FPC, the warpage of the FPC after baking is small, and no halogen compound is added. Providing a polyimide precursor, a photosensitive polyimide precursor composition, a photosensitive dry film, and a flexible printed wiring board using them which express flame retardance. The polyimide precursor of this invention contains the acid dianhydride represented by following General formula (1), It is characterized by the above-mentioned.

(X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms. R ₁ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.)

Description

Polyimide precursor, photosensitive polyimide precursor composition, photosensitive dry film, and flexible printed wiring board using them {POLYIMIDE PRECURSOR, PHOTOSENSITIVE POLYIMIDE PRECURSOR COMPOSITION, PHOTOSENSITIVE DRY FILM, AND FLEXIBLE PRINTED CIRCUIT BOARD USING THOSE MATERIALS}

The present invention relates to a polyimide precursor, a photosensitive polyimide precursor composition, a photosensitive dry film and a flexible printed wiring board using them.

In recent years, a film-shaped printed board called a flexible printed board (hereinafter also referred to as "FPC") has been booming. This board has a structure having a coverlay made of polyimide film or the like on a wired FCCL (Flexible Cupper Clad Laminate), and is mainly used in devices such as mobile phones, notebook computers, digital cameras, and the like. The FPC is indispensable for miniaturization and weight reduction because the FPC maintains its function even after bending. In particular, in recent years, miniaturization and lightening of electronic devices represented by notebook computers have been progressed, and by adopting FPC to such products, it has contributed to reducing the size and weight of the device, reducing product cost, and simplifying the design. .

The coverlay provided in this FPC is formed by bonding together using the polyimide film etc. which were mainly equipped with an adhesive agent. However, as the FPC becomes smaller and thinner, a problem arises in the positional accuracy of the bonding. Therefore, the development of the photosensitive coverlay which can process only the necessary part finely and finely by irradiating active light, such as an ultraviolet-ray, began to be actively made. Among them, the dry film type photosensitive coverlay exhibits excellent dimensional accuracy and does not require a drying step of the solvent, so that the process can be simplified in FPC production and is expected as a material having low environmental load.

Among photosensitive coverlay materials, photosensitive coverlays using polyimide precursors are expected as excellent coverlays from the viewpoints of bending resistance, heat resistance and electrical insulation derived from polyimide. For example, Patent Document 1 discloses a heat resistant adhesive agent using tetracarboxylic dianhydride and diamine. In addition, Patent Document 2 discloses a film-forming photosensitive heat resistant resin composition using a polyimide precursor, and Patent Document 3 discloses a photosensitive cover coat material containing a polyamic acid. In addition, Patent Document 4 discloses an adhesive film made of a specific acid dianhydride. However, in the case of the photosensitive coverlay using these polyimide precursors, the molecular weight of the polyimide precursor fell by the problem of the tackiness of the photosensitive dry film, and the desolvent accompanying photosensitive dry film formation, and the photosensitive dry film obtained was bent. At this time, there may be a problem that the photosensitive layer is cracked. Furthermore, when the molecular weight of a polyimide precursor falls, when developing a pattern by lithography, in image development using aqueous alkali solution, image development time is not stabilized, the film thickness of a pattern becomes thin, a pattern shape deforms, etc. Occurs. Moreover, in the process of converting a polyimide precursor into a polyimide, curvature may arise in FPC because of the stress resulting from the desolvent and the waste-ring reaction accompanying the imidation of a polyimide precursor. If warpage occurs in the FPC, problems such as poor adhesion between the FCCL and the coverlay and high driving power of the electronic device provided with the FPC will occur. Therefore, it is desired to improve the warpage of the FPC provided with the coverlay on the copper wiring.

In addition, the coverlay is required to express flame retardancy in the flame retardancy test represented by the VTM test of UL standard. For the purpose of expressing flame retardancy, halogen compounds have been blended with the original coverlay. However, it is desired to express flame retardancy with non-halogen from the viewpoint of environmental conservation or from the viewpoint of biotoxicity.

Japanese Unexamined Patent Publication No. 2004-269622 Japanese Patent Application Laid-Open No. 04-18450 Japanese Patent Application Laid-Open No. 05-158237 Japanese Unexamined Patent Publication No. 10-330723

This invention is made | formed in view of such a point, and when used for FPC, the polyimide precursor, the photosensitive polyimide precursor composition, the photosensitive dry film, and the flexible printed wiring board which used the FPC after baking which were few in the bending of FPC, and were excellent in bendability The purpose is to provide.

The polyimide precursor of this invention contains the acid dianhydride represented by following General formula (1), It is characterized by the above-mentioned.

[Formula 1]

(X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms. R ₁ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.)

In the polyimide precursor of this invention, it is preferable to contain the diamine represented by following General formula (2).

[Formula 2]

(Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. R ₂ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.)

In the polyimide precursor of this invention, it is preferable to contain the acid dianhydride represented by following General formula (3).

(3)

(a represents an integer of 1 to 20. b represents an integer of 3 to 30. R ₃ represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms)

In the polyimide precursor of this invention, it is preferable to contain the diamine represented by following General formula (4).

[Formula 4]

(Z is an alkylene group having 2 to 20 carbon atoms. R ₄ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group. C represents an integer of 2 to 30.)

In the polyimide precursor of this invention, it is preferable to contain the acid dianhydride represented by following General formula (3).

[Chemical Formula 5]

(a represents an integer of 1 to 15. b represents an integer of 5 to 20. R ₃ represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms)

In the polyimide precursor of this invention, it is preferable that the diamine represented by the said General formula (4) is 25 mol%-75 mol% in all the diamine components.

The photosensitive polyimide precursor composition of this invention contains 100 mass parts of said polyimide precursors, and 5-30 mass parts of photosensitizers, It is characterized by the above-mentioned.

In the photosensitive polyimide precursor composition of this invention, it is preferable that the said photosensitive agent contains a quinonediazide structure.

In the photosensitive polyimide precursor composition of this invention, it is preferable to contain the compound which has a phenolic hydroxyl group as a dissolution inhibiting agent.

The photosensitive dry film of this invention is characterized by apply | coating and desolventing the said photosensitive polyimide precursor composition to a support film, and then laminating | stacking a cover film. It is characterized by the above-mentioned.

The flexible printed wiring board of this invention is formed using the said photosensitive dry film, It is characterized by the above-mentioned.

The polyimide precursor of this invention is characterized by the ratio (Mw2 / Mw1) between the weight average molecular weight (Mw1) in a varnish and the weight average molecular weight (Mw2) after desolvent at 120 degrees C or less is 0.7 or more.

When the photosensitive polyimide precursor composition of this invention uses the polyimide precursor obtained from the acid dianhydride which has a specific structure, when it is used for FPC, there exists little curvature of FPC after baking, and shows the effect that it is excellent in bendability.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

(A) polyimide precursor

Acid dianhydride and diamine are used as a monomer of a polyimide precursor. It is known that the molecular weight of the polyimide precursor is lowered by a desolvent accompanied by heating. However, as an acid dianhydride used for the polyimide precursor, an acid represented by the following general formula (1) is used in view of reducing the decrease in molecular weight. 2 Use anhydrides. As long as it is an acid dianhydride represented by the said structure, you may use individually or it may use in combination of 2 or more types. By suppressing the molecular weight fall in a desolvent process, the crack at the time of bending when it is set as the photosensitive dry film can be prevented, and bendability can be improved.

[Formula 6]

(X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms. R ₁ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.)

Among these, it is preferable to use the acid dianhydride represented by following General formula (3) from a viewpoint of suppressing molecular weight fall in a desolvent process.

[Formula 7]

(a represents an integer of 1 to 20. b represents an integer of 3 to 30. R ₃ represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms)

In acid dianhydride represented by the said General formula (3), 1-15 are preferable and, as for b, 5-20 are preferable. Specifically, butanediol-bis- anhydrous trimellitic acid ester, pentanediol-bis- anhydrous trimellitic acid ester, heptanediol-bis- anhydrous trimellitic acid ester, decanediol-bis-trim anhydride ester, and icosane diol -Bis- trimellitic anhydride, polypropylene diol-bis-trimellitic anhydride, polytetramethylenediol-bis-trimellitic anhydride, etc. are mentioned. These compounds may be used alone or in combination of two or more thereof.

In addition to the said acid dianhydride, other acid dianhydride can also be used for the polyimide precursor which concerns on this invention. Specifically, as aromatic tetracarboxylic acid, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3', 4'-biphenyl tetracarr Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3, 3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis ( 2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,3'-oxydiphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, 4- (2,5-di Sotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-bis (3,4-dicarboxyphenoxy ) Biphenyl dianhydride, ethylenediol-bis- anhydride trimellitic acid ester, etc. are mentioned.

As aliphatic tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5,6-cyclohexane tetracarboxylic acid Dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] And octo-7-ene-2,3,5,6 tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride. It is preferable to use these acid dianhydrides in the range of 0 mol%-50 mol% with respect to the acid dianhydride whole quantity of a polyimide precursor from a viewpoint of reducing the curvature after baking.

As a diamine used for a polyimide precursor, the diamine represented by following General formula (2) is used from a viewpoint which suppresses molecular weight fall in a desolvent process, and a viewpoint to improve tackiness when it sets it as a photosensitive dry film after a desolvent. It is desirable to. As long as it is a diamine represented by the said structure, you may use individually or it may use in combination of 2 or more types. In the following General Formula (2), R ₂ is preferably a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms.

[Formula 8]

(Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. R ₂ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.)

Specifically, dimethylene-bis (2-aminobenzoate), dimethylene-bis (3-aminobenzoate), dimethylene-bis (4-aminobenzoate), trimethylene-bis (2-aminobenzoate ), Trimethylene-bis (3-aminobenzoate), trimethylene-bis (4-aminobenzoate), tetramethylene-bis (2-aminobenzoate), tetramethylene-bis (3-aminobenzoate), Tetramethylene-bis (4-aminobenzoate), 3-methyltetramethylene-bis (2-aminobenzoate), 3-methyltetramethylene-bis (3-aminobenzoate), 3-methyltetramethylene-bis ( 4-aminobenzoate), pentamethylenebis (2-aminobenzoate), pentamethylenebis (3-aminobenzoate), pentamethylenebis (4-aminobenzoate), decamethylene-bis (2-aminobenzoate ), Decamethylene-bis (3-aminobenzoate), decamethylene-bis (4-aminobenzoate), and the like. have. These diamines may be used alone or in combination of two or more thereof.

Moreover, especially, using the compound represented by following General formula (4) is preferable from a viewpoint of suppressing molecular weight fall in a desolvent process, and a viewpoint of improving tackiness, when using it as a photosensitive dry film after a desolvent.

[Formula 9]

(Z is an alkylene group having 2 to 20 carbon atoms. R ₄ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group. C represents an integer of 2 to 30.)

Specifically, polydimethylene oxide-di-o-aminobenzoate), polydimethylene oxide-di-m-aminobenzoate, polydimethylene oxide-di-p-aminobenzoate, polytrimethylene oxide-di -o-aminobenzoate, polytrimethylene oxide-di-m-aminobenzoate, polytrimethylene oxide-di-p-aminobenzoate, polytetramethylene oxide-di-o-aminobenzoate, polytetramethylene oxide -Di-m-aminobenzoate, polytetramethylene oxide-di-p-aminobenzoate, poly-3-methyltetramethylene oxide-di-o-aminobenzoate, poly-3-methyltetramethylene oxide-di- m-aminobenzoate, poly-3-methyltetramethylene oxide-di-p-aminobenzoate, polypentamethylene oxide-di-o-aminobenzoate, polypentamethylene oxide-di-m-aminobenzoate, poly Pentamethyl Oxide-di-p-aminobenzoate, polydecamethylene oxide-di-o-aminobenzoate, polydecamethylene oxide-di-m-aminobenzoate, polydecamethylene oxide-di-p-aminobenzoate, poly (Tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate) etc. are mentioned. These diamines may be used alone or in combination of two or more thereof.

Moreover, it is preferable that the diamine represented by the said General formula (4) is 25 mol%-75 mol% in all the diamine components from a viewpoint of reducing the curvature after baking in the compounding quantity of these diamine.

In particular, it is preferable to use the compound represented by the said General formula (2) and the compound represented by the said General formula (4) simultaneously. When using the compound represented by the said General formula (2) and the compound represented by the said General formula (4) simultaneously, the reduction of curvature, the improvement of the tackiness at the time of setting it as a photosensitive dry film after a solvent, and a viewpoint of favorable lithography characteristic It is preferable that the compounding quantity of the compound represented by the said General formula (4) is 25 mol%-75 mol% with respect to diamine whole quantity.

Moreover, it is possible to use the said diamine and other diamine simultaneously. Specifically 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3 , 4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (Trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diaminodimethylbenzothiophen-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-dia Minobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 1, n-bis (4-aminophenoxy Alkanes, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis ( 4-aminophenyl) fluorene, 5 (6) -amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy ) Biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3,3'-dicarboxy-4,4'- Diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 1,4-bis (4-amino Phenoxy) pentane, 1,5-bis (4'-aminophenoxy) pentane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4 -Aminobutyl) tetramethyl disiloxane, bis ((gamma) -aminopropyl) tetraphenyl disiloxane, the diamino siloxane compound represented by following General formula (5), etc. are mentioned. These may be used independently or may be used in combination of 2 or more type. It is preferable to mix | blend these diamine with 0 mol%-50 mol% with respect to the total mole number of diamine from a viewpoint of reducing curvature after baking.

[Formula 10]

When synthesize | combining a polyimide precursor, you may seal a polyimide precursor terminal using monofunctional acid anhydride, monofunctional carboxylic acid, and monofunctional amine as needed.

Moreover, it is also possible to esterify a part of carboxyl group of the polyimide precursor which concerns on this invention using well-known compounds, such as an alcohol compound, and a method.

The polyimide precursor which concerns on this invention can be set as the photosensitive polyimide precursor composition by mix | blending (B) photosensitive agent and (C) organic solvent.

(B) photosensitizer

The photosensitive polyimide precursor composition which concerns on this invention mix | blends the compound which generate | occur | produces an acid by irradiating actinic light as a photosensitive agent. The photosensitive agent is not particularly limited as long as an acid is generated by irradiation with active light, but is preferably a compound containing a quinone diazide structure such as a benzoquinone diazide compound and a naphthoquinone diazide compound. For example, those described in US Pat. No. 2797213 and US Pat. No. 3669658 can be used. Especially, the ester compound of a phenol compound and 1,2-naphthoquinone-2- diazide-4-sulfonic acid, or 1,2-naphthoquinone-2- diazide-5-sulfonic acid is preferable. These may be used independently or may be used in combination of 2 or more types.

5 mass parts-35 mass parts are preferable with respect to 100 mass parts of polyimide precursors, and, as for the compounding quantity of the photosensitive agent which concerns on this invention, 10 mass parts-30 mass parts are more preferable. As for the compounding quantity of a photosensitive agent, 5 mass parts or more are preferable from a viewpoint of photosensitive expression and the inhibition of dissolution to the developing solution which consists of aqueous alkali solution, and 35 mass parts or less from a viewpoint of a sensitivity and toughness expression of a coverlay.

(C) organic solvent

Examples of the organic solvent used in the present invention include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, and dimethyl sulfoxide. have. Moreover, the solvent which is lower boiling point than these solvent can be mix | blended as needed. By mix | blending a low boiling point solvent, foaming at the time of drying can be suppressed. Specifically as a low boiling point solvent, ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or hexylene Alcohols such as glycols, ethers such as 1,4-dioxane, trioxane, diethylacetal, 1,2-dioxolane, diethylene glycol dimethyl ether, tetrahydrofuran, anisole and triethylene glycol dimethyl ether , Ethyl acetate, methyl benzoate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, propylene glycol monobutyl ether acetate Esters such as dihydrate, propylene glycol diacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate, n-heptane, n-octane, cyclohexane, benzene, toluene, xylene And hydrocarbons such as ethylbenzene and diethylbenzene. 25 mass parts-900 mass parts are preferable with respect to 100 mass parts of polyimide precursors, and, as for the compounding quantity of an organic solvent, 100 mass parts-400 mass parts are more preferable. If the blending amount is more than 900 parts by mass, it is difficult to maintain the film thickness after application, and if it is less than 25 parts by mass, the polyimide precursor is not completely dissolved.

(D) dissolution inhibitor

The dissolution inhibiting agent can be mix | blended with the photosensitive polyimide precursor composition which concerns on this invention as needed. By mix | blending a dissolution inhibiting agent, dissolution with respect to the developing solution which consists of aqueous alkali solution of a polyimide precursor can be suppressed. The dissolution inhibiting agent which concerns on this invention means the compound which hydrogen-bonds with the carboxyl group and phenolic hydroxyl group of a polyimide precursor. When the carboxyl group and phenolic hydroxyl group of the polyimide precursor are hydrogen-bonded with a dissolution inhibitor, it is shielded from a developing solution, and it becomes possible to suppress dissolution of a polyimide precursor with hydrophobicity of the said compound.

As a compound which has a group which carries out hydrogen bond with a carboxyl group and a phenolic hydroxyl group, a carboxylic acid compound, a carboxylic ester compound, an amide compound, a urea compound, etc. are mentioned. From the viewpoint of the dissolution inhibiting effect and the storage stability of the developer composed of the aqueous alkali solution, the compound represented by the following General Formula (6) is preferable, and an amide compound and a urea compound are more preferable.

[Formula 11]

(R ₅ and R ₆ represent an organic group consisting of all or part of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. R ₅ and R ₆ may be the same or different.)

As the amide compound, for example, N, N-diethylacetamide, N, N-diisopropylformamide, N, N-dimethylbutylamide, N, N-dibutyl acetamide, N, N-di Propylacetamide, N, N-dibutylformamide, N, N-diethylpropionamide, N, N-dimethylpropionamide, N, N'-dimethoxy-N, N'-dimethyloxamide, N-methyl -ε-caprolactam, 4-hydroxyphenylbenzamide, salicylamide, salicylicanilide, acetanilide, 2'-hydroxyacetanilide, 3'-hydroxyacetanilide, 4'-hydroxyacetanilide Can be.

Especially, the compound which has a phenolic hydroxyl group is preferable from a viewpoint of the low glass transition point of the film obtained by baking the photosensitive layer and the said photosensitive layer, control of the solubility with respect to the developing solution which consists of aqueous alkali solution, and high residual film rate, and it is phenolic The amide compound which has a hydroxyl group is more preferable. Specifically, 4-hydroxyphenyl benzamide, 2'-hydroxyacetanilide, 3'-hydroxyacetanilide, and 4'-hydroxyacetanilide are mentioned. These may be used independently or may be used in combination of 2 or more type.

As a urea compound, 1, 3- dimethyl urea, tetramethyl urea, tetraethyl urea, 1, 3- diphenyl urea, 3-hydroxyphenyl urea is mentioned, for example. Especially, the urea compound containing a phenolic hydroxyl group is more preferable from a viewpoint of the control of solubility to the developing solution which consists of aqueous alkali solution, the high residual film ratio, the photosensitive layer, and the low glass transition point of the film obtained by baking this photosensitive layer. . Specifically, 3-hydroxyphenyl urea is mentioned. These may be used independently or may be used in combination of 2 or more type.

When using an amide compound, the dissolution inhibiting agent which concerns on this invention mix | blends 0.1 mol-2.0 mol with respect to the expression of a dissolution inhibiting effect with respect to 1 mol of carboxyl groups and phenolic hydroxyl groups of a polyimide precursor, and it is 0.15 mol It is more preferable to mix | blend-1.5 mol.

When using a urea compound, the dissolution inhibiting agent which concerns on this invention has preferable 0.1 mol-2.0 mol from a viewpoint of expression of a dissolution inhibiting effect with respect to 1 mol of carboxyl groups and phenolic hydroxyl groups of a polyimide precursor. It is more preferable to mix | blend 0.15 mol-1.5 mol from a viewpoint of toughness expression of resin obtained by dissolution inhibiting effect expression and baking.

Moreover, when using both an amide compound and a urea compound, the total amount of an amide compound and a urea compound is 0.1 mol-1.5 mol with respect to 1 mol of carboxyl groups and phenolic hydroxyl groups of a polyimide precursor from a viewpoint of a dissolution inhibiting effect. Range is preferred.

(E) phenolic compounds

A phenol compound can be mix | blended with the photosensitive polyimide precursor composition of this invention as needed. A phenolic compound is a phenolic compound containing the compound represented by following General formula (7) and the structure of following General formula (8) from a viewpoint of the curvature reduction of the sheet | seat which consists of a film after baking, and a solubility control with respect to aqueous alkali solution. (We assume ingredient which does not correspond to dissolution inhibitor of this application).

[Formula 12]

(R ₇ and R ₈ each independently represent a hydrogen atom or an organic group having 1 to 50 carbon atoms and an oxygen atom 0 to 10. X each independently represents a hydrogen atom or a hydroxyl group or an organic group having 1 to 20 carbon atoms)

[Formula 13]

(R ₉ and R ₁₁ each independently represent an organic group having 1 to 6 carbon atoms, and R ₁₀ represents a bonding group or an organic group having 1 to 20 carbon atoms)

Specifically, dihydroxy diphenylmethane, 4,4'- oxydiphenol, 1, 4-bis- (3-hydroxyphenoxy) -benzene, 1, 3-bis- (4-hydroxyphenoxy 2) such as) -benzene, 1,5-bis- (o-hydroxyphenoxy) -3-oxapentane, α, α'-bis- (4-hydroxyphenyl) -1,4-diisopropylbenzene 3 such as nucleus, tris (hydroxyphenyl) methane, tris (hydroxyphenyl) ethane, 4- {4- [1,1-bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} phenol A nucleus body, the polynuclear body represented by the following structural formula group (a), etc. are mentioned. These phenolic compounds may be used independently or may be used in combination of 2 or more type.

[Formula 14]

1 mass part-30 mass parts are preferable with respect to 100 mass parts of polyimide precursors, and, as for the compounding quantity of the phenolic compound which concerns on this invention, 5 mass parts-20 mass parts are more preferable. When the blending amount is less than 1 part by mass, it is difficult to inhibit the solubility in a developer composed of an aqueous alkali solution. When the blending amount is more than 30 parts by mass, the photosensitive layer of the photosensitive dry film obtained after the desolvent process becomes weak.

(F) plasticizer

In the photosensitive polyimide precursor composition which concerns on this invention, the compound represented by following General formula (9) can also be used suitably as a plasticizer.

[Formula 15]

(R ₁₂ to R ₁₄ are organic groups containing an ethylene glycol chain and / or a propylene glycol chain, which may be the same as or different from each other)

Although the compound specifically, shown by following structural formula (i) and (j) is mentioned, It is not limited to this. In addition, these compounds may be used independently or may be used in combination of 2 or more type.

[Formula 16]

(d is an integer greater than or equal to 0, e is an integer greater than or equal to 0)

1 mass part-30 mass parts are preferable with respect to 100 mass parts of polyimide precursors, and, as for the compounding quantity of the plasticizer which concerns on this invention, 1 mass part-10 mass parts are more preferable. If the blending amount is 1 part by mass or more, the warpage reduction effect is expressed, and if it is 30 parts by mass or less, a desired pattern is obtained without adversely affecting developability.

(G) crosslinking agent

In this invention, a crosslinking agent can be mix | blended for the purpose of improving the toughness of the film after baking. As a crosslinking agent, the tetracarboxylic-acid compound or tetracarboxylic-acid ester compound represented by following General formula (10), and the polyimide precursor or carboxyl group-containing polyimide precursor ester compound represented by following General formula (11) are preferable.

[Formula 17]

(R ₁₅ is a tetravalent organic group, R ₁₆ to R ₁₉ are hydrogen or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different.)

[Formula 18]

_{(R 20, R 22, R} 24 is also even and, different from the same respectively as the tetravalent organic group. R _21, R ₂₃ is also even and, different from the same respectively as the divalent organic group. R ₂₅ To R ₃₂ are hydrogen or a monovalent organic group having 1 to 20 carbon atoms, which may be the same or different, respectively, g is an integer of 0 to 100)

0.1 mol-1.5 mol are preferable, and, as for the compounding quantity of the crosslinking agent which concerns on this invention from the viewpoint of the expression of a crosslinking effect with respect to the mole number of the remaining amino group of a polyimide precursor, 0.5 mol-1.1 mol are more preferable. The amount of remaining amino groups can be calculated using high performance liquid chromatography.

(H) thermal base generator

The photosensitive polyimide precursor composition which concerns on this invention can contain a thermal base generator as needed. A thermal base generator is a compound which generates a base by heating. For example, it is obtained by making a salt structure with the amino group of base compounds, such as an amine, and acids, such as a sulfonic acid, protecting by a dicarbonate compound and protecting by an acid chloride compound. Thereby, at room temperature, it is stable without expressing basicity, and it can be set as the thermal base generator which deprotects by heating and produces | generates a base. Moreover, the temperature of baking of a polyimide precursor can also be made comparatively low by mix | blending the said thermal base generator.

Specifically as a thermal base generating agent, U-CAT (trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851 (above, brand name San Apro Corporation), N- (isopropoxycarbonyl ) -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, aromatic The compound etc. which protected the amino group of diamine with dibutyl dicarbonate are mentioned. Among them, N- (isopropoxycarbonyl) -2,6-dimethylpiperidine, N- (tert) from the viewpoint of the storage stability of the photosensitive polyimide precursor composition, molecular weight stability by desolvent, alkali solubility, and ion migration properties. Amino group of -butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) -2,6-dimethylpiperidine, 4,4-diaminodiphenylether dibutyl dicarbonate The compound protected with the compound, the compound which protected the amino group of 3,4'- diamino diphenyl ether with dibutyl dicarbonate, and the amino group of 1, 3-bis (3-aminophenoxy) benzene protected by dibutyl dicarbonate. Compound, The compound which protected the amino group of 1, 3-bis (4-aminophenoxy) benzene with dibutyl dicarbonate, The compound which protected the amino group of trimethylene-bis (4-amino benzoate) with dibutyl dicarbonate, Preference is given to compounds in which the amino group of 1,4-bis (4-aminophenoxy) pentane is protected with dibutyl dicarbonate. The compound can be synthesized, for example, by the known method described in Chmistry Letters Vol. 34, No. 10 (2005).

From the viewpoint of the promotion of imidization and the development performance, the blending amount of the thermal base generator according to the present invention is preferably 0.5 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor. Do.

(I) Phosphate Ester Compound

A phosphate ester compound can be mix | blended with the photosensitive polyimide precursor composition which concerns on this invention as needed. These compounds act as a flame retardant, a dissolution aid, or a plasticizer with respect to the photosensitive polyimide precursor composition.

As the phosphate ester compound, at least one compound selected from the group consisting of compounds represented by the following general formula (12), the following general formula (13) or the following general formula (14) is used.

[Formula 19]

(R ₃₃ to R ₃₅ represent an organic group having 1 or more carbon atoms, and may be the same or different, respectively.)

[Formula 20]

(R ₃₆ to R ₃₉ represent an organic group having 1 or more carbon atoms, and may be the same or different from each other.)

[Formula 21]

(Wherein R ₄₀ is hydrogen or a monovalent organic group)

In consideration of improving the flame retardancy and plasticity of the photosensitive polyimide precursor composition, R ₃₃ to R ₃₅ in General Formula (12) or R ₃₆ to R ₃₉ in General Formula (13) are a methyl group, an ethyl group, a butyl group, or 2 It is preferable that it is an organic group chosen from an ethylhexyl group, butoxyethyl group, a phenyl group, a cresyl group, a xylenyl group, and an aminophenyl group.

In addition, considering the thermal stability and the warpage improvement effect of the photosensitive dry film, R ₄₀ in the general formula (14) is a hydrogen, a dihydroxyphenyl group, a dibutylhydroxybenzyl group, a (meth) acrylate-containing organic group. It is preferable that it is an organic group chosen. In addition, considering that the effect of improving the bending when the screen compatible or photosensitive dry film of the resin varnish and R ₄₀ is preferably hydrogen.

These phosphate ester compounds can be mix | blended individually or in combination of 2 or more types. 1 mass part-30 mass parts are preferable, and, as for the compounding quantity of these phosphate ester compounds, 1 mass part-20 mass parts are more preferable. If the blending amount is 1 part by mass or more, plasticity is expressed, and when the blending amount is 30 parts by mass or less, the portion which does not irradiate the actinic light of the photosensitive polyimide precursor composition does not erode well to the developing solution composed of an aqueous alkali solution, thereby providing a good linearity. You can get it.

(J) organophosphorus compounds

The organophosphorus compound represented by following General formula (15) can be mix | blended with the photosensitive polyimide precursor composition which concerns on this invention. By mix | blending the said organic phosphorus compound, flame retardance can be provided to the resin pattern obtained by baking.

[Formula 22]

(R ₄₁ represents an organic group. H represents an integer of 1 to 50)

1 mass part-30 mass parts are preferable, and, as for the compounding quantity of these organophosphorus compounds, 3 mass parts-25 mass parts are more preferable. If the blending amount is at least 1 part by mass, flame retardancy is expressed, and if it is at most 30 parts by mass, the resin pattern obtained after baking is tough.

(K) other ingredients

An imidazole compound, a triazole compound, a tetrazole compound, and a sulfide compound can be mix | blended with the photosensitive polyimide precursor composition which concerns on this invention as needed. By mix | blending these compounds, adhesiveness with a copper substrate can be improved.

0.1 mass part-10 mass parts are preferable, and, as for the compounding quantity of these compounds, 0.1 mass part-5 mass parts are more preferable. If the compounding quantity is 0.1 mass part or more, the adhesive improvement effect will be expressed, and if it is 10 mass parts or less, it will not adversely affect developability and can obtain favorable linear form.

In the photosensitive polyimide precursor composition which concerns on this invention, alcohol, such as ethanol, 2-propanol, ethylene glycol, ethyl lactate, methyl benzoate, ethylene glycol monopropyl ether acetate as needed for the purpose of improving the wettability with a support film. Esters such as methyl, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as n-butyl ether, tetrahydrofuran and dioxane, glycol ethers such as ethylene glycol monoethyl ether and propylene glycol monoethyl ether It can mix.

The photosensitive polyimide precursor composition of this invention can be used as a coverlay. A coverlay is a protective film which protects the wiring formed on a silicon wafer, a copper clad laminated board, FPC, etc.

(Combination of Photosensitive Polyimide Precursor Composition)

The photosensitive polyimide precursor composition which concerns on this invention mix | blends the said polyimide precursor and various compounds in a suitable container, until it melt | dissolves completely by the mixing rotor, the non-bubbling kneader, the three-one motor with a stirring blade, etc. It is obtained by stirring.

(Manufacture of Resin Patterns)

In this invention, a photosensitive dry film can be produced using the photosensitive polyimide precursor composition, and a resin pattern can be formed. The said resin pattern can be formed in the following process.

(1) Process of apply | coating photosensitive polyimide precursor composition to a film base material, and then desolventing to make a photosensitive dry film.

The photosensitive dry film is obtained by apply | coating the photosensitive polyimide precursor composition to a support film (film base material), drying a solvent, and forming a photosensitive layer. As the support film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyallylate, polyacrylonitrile, ethylene / cyclodecene copolymer and the like can be used. These supporting films can be subjected to surface treatment for the purpose of controlling the wettability of the photosensitive polyimide precursor composition and the peelability of the photosensitive layer obtained from the photosensitive polyimide precursor composition. As a surface treatment method, surface modification using a corona treatment, a frame treatment, a plasma treatment, silicone, an alkyd resin, an olefin resin, etc. are mentioned. The thickness of the carrier film is usually 15 µm to 100 µm, preferably 15 µm to 75 µm in consideration of applicability, adhesion, rollability, toughness, cost, and the like.

Application | coating of the photosensitive polyimide precursor composition can be performed to the said support film using well-known methods, such as a reverse roll coater, a gravure roll coater, a comma coater, a lip coater, and a slot die coater.

A desolvent can be performed by drying a solvent (dryer using hot air drying, far infrared rays, and near infrared rays). From a viewpoint of suppressing molecular weight fall, a drying temperature has preferable temperature of 50 degreeC-120 degreeC, and 50 degreeC-110 degreeC is further more preferable from the viewpoint of stability of a photosensitive agent. As for the film thickness of the photosensitive layer obtained by the desolvent, 5 micrometers-100 micrometers are preferable, More preferably, they are 5 micrometers-50 micrometers. As for a film thickness, 5 micrometers or more are preferable from a viewpoint of insulation reliability, and 100 micrometers or less are preferable from a viewpoint of obtaining a favorable linear form. Here, when the ratio (Mw2 / Mw1) between the weight average molecular weight (Mw1) in a polyimide precursor varnish and the weight average molecular weight (Mw2) after desolvation at 120 degrees C or less is 0.7 or more, the photosensitive dry film after a solvent will be bent. Even if the photosensitive layer is not cracked, it is effective.

Moreover, a cover film is laminated | stacked on the photosensitive dry film, and it can be set as a photosensitive laminated film. By laminating the cover film, the photosensitive layer can be prevented from adhering to the support film. As the cover film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyallylate, polyacrylonitrile, ethylene / cyclodecene copolymer can be used.

(2) Process of crimping | stacking a photosensitive dry film on the board | substrate which arrange | positioned the pattern, and forming a photosensitive layer.

The photosensitive dry film is superposed on a surface (on a substrate on which a pattern is arranged) on which a circuit such as an FPC is formed, and it is 40 ° C to 130 ° C, preferably 60 ° C to 60 ° C by a known method such as planar laminate, roll laminate, or vacuum press. The photosensitive layer can be laminated by laminating (pressing) at a pressure of 0.2 MPa to 5 MPa while heating at 120 ° C.

At this time, when the photosensitive dry film is a photosensitive laminated film which laminated | stacked the cover film, a cover film is peeled off before lamination. By setting the laminating temperature to 40 ° C or higher, it takes no time due to the tack during the alignment before the lamination. When the laminating temperature is set to 130 ° C or lower, decomposition of the photosensitive agent does not proceed and the lamination can be performed. In addition, the laminating temperature means a temperature at which the photosensitive layer can be controlled at a viscosity at which the filling of the pattern can be sufficiently filled without problems such as bubble residue and the photosensitive polyimide precursor composition is excessively flowed to flow out of the pattern. it means.

Moreover, lamination of the photosensitive dry film can be performed suitably by making glass transition point (hereinafter Tg) of a photosensitive layer lower than lamination temperature. After laminating the photosensitive layer, the supporting film may or may not be peeled off. When a support film is not peeled off after lamination, it peels after an exposure process.

(3) Process of irradiating actinic light to photosensitive layer

The photosensitive layer is exposed through a photomask on which an arbitrary pattern is drawn to form fine pores or fine width lines. Although exposure amount changes with the composition of the photosensitive polyimide precursor composition, it is 100 mJ / cm <2> -3,000 mJ / cm <2> normally. Examples of the active light used at this time include X-rays, electron beams, ultraviolet rays, visible rays, and the like. As a light source of active light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, etc. can be used. In this invention, it is preferable to use the i line | wire (365 nm), h line | wire (405 nm), and g line | wire (436 nm), such as a mercury lamp. As a method of irradiating an actinic light, any of a close exposure and a projection exposure may be sufficient.

(4) Process to develop by aqueous alkali solution

After exposure, image development can be performed by a well-known method, such as an immersion method and a spray method, using a developing solution, and a linear form can be obtained. As a developing solution, alkaline aqueous solutions, such as aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, and tetramethylammonium hydroxide aqueous solution, can be used. Moreover, in this process, it is preferable to develop, heating a developing solution. By managing development temperature, development time can be controlled and the linear shape obtained can be maintained. From these viewpoints, 20 degreeC-60 degreeC is preferable and 25 degreeC-50 degreeC of the temperature of a developing solution is more preferable.

(5) Rinsing with at least one solvent selected from the group consisting of water and acidic aqueous solution

After image development, it washes by well-known methods, such as an immersion method and a spray method. As a rinse liquid, what added the organic solvent to water or water can be used. In this step, it is preferable to maintain the rinse liquid at an appropriate temperature. This makes it possible to eliminate residues on the substrate or the resin after development. As temperature of a rinse liquid, 15 degreeC-60 degreeC is preferable from a viewpoint of residue removal, and 20 degreeC-50 degreeC are more preferable. After washing with a rinse liquid, the inorganic acid aqueous solution or the organic acid aqueous solution may be washed. Specific examples of the inorganic acid aqueous solution include hydrochloric acid aqueous solution, sulfuric acid aqueous solution, phosphoric acid aqueous solution and boric acid aqueous solution. Specific examples of the organic acid aqueous solution include formic acid aqueous solution, acetic acid aqueous solution, citric acid aqueous solution, and lactic acid aqueous solution. From the viewpoint of the cleaning efficiency, the cleaning time using the inorganic acid aqueous solution or the organic acid aqueous solution is preferably 5 seconds to 120 seconds, and more preferably 10 seconds to 60 seconds. When rinsing with an acidic aqueous solution, it is preferable to rinse the acidic aqueous solution with water after that.

(6) Process of irradiating actinic light to the whole photosensitive layer

You may irradiate an active light beam to the whole linear surface obtained after a rinse process. By decomposing a photosensitive agent by this process, the time taken in a subsequent curing process can be shortened. Furthermore, the light transmittance of the resin pattern obtained after a curing process can be raised.

Moreover, by this process, the residual stress applied between the photosensitive agent-derived board | substrate and the photosensitive layer can be reduced, the curvature of the FPC obtained by a resin pattern manufacturing process, or a multilayer printed wiring board can be reduced, and a corrosion resistance can be improved. Although the exposure amount irradiated by this process changes with kinds of the photosensitive agent to be used, and the film thickness of the photosensitive layer, it is 100 mJ / cm <2> -3,000 mJ / cm <2> normally. For example, when the film thickness of a photosensitive layer is 25 micrometers using a naphthoquinone diazide compound as a photosensitive agent, 500 mJ / cm <2> or more is preferable from a photolysis viewpoint of a photosensitive agent. Examples of the active light used at this time include X-rays, electron beams, ultraviolet rays, visible rays, and the like. As a light source of active light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, etc. can be used. Among these, it is preferable to use i line | wire (365 nm), h line | wire (405 nm), and g line | wire (436 nm), such as a mercury lamp. Moreover, actinic light can be irradiated as needed while heating. From a viewpoint of workability, 30 degreeC-130 degreeC is preferable and 40 degreeC-100 degreeC are more preferable.

(7) Baking at 100 to 400 ° C

The resin pattern is formed by baking on the line obtained by the said process. Bake is carried out continuously or stepwise for 5 minutes to 5 hours at a temperature of 100 ° C to 400 ° C. Then, the finished product is completed. In the case of FPC, it is preferable to cure in the temperature range of 100 to 200 degreeC from the oxidation prevention viewpoint of wiring. As the processed product obtained in this way, an FPC, a multilayer printed wiring board, etc. may be mentioned.

Example

Hereinafter, although this invention is demonstrated concretely according to an Example, it is not limited at all by these examples.

Synthesis of Polyimide Precursor

Synthesis Example 1 Synthesis of Polyimide Precursor (i)

6.4 g of 1,3-bis (3-aminophenoxy) benzene and 62 g of γ-butyrolactone were put into a three-neck separable flask and stirred until a homogeneous solution was obtained. Next, 10 g of pentanediol bis-trim anhydride ester was added, and the mixture was stirred for 1 hour while cooling with ice, and then at room temperature for 6 hours. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (i) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (i), solid content of a solution of the polyimide precursor (i), and a weight average molecular weight are shown in Table 1.

Synthesis Example 2 Synthesis of Polyimide Precursor (ii)

Into a three-neck separable flask, 4.8 g of 1,3-bis (3-aminophenoxy) benzene, 6.8 g of polytetramethylene oxide-di-p-aminobenzoate, and 82 g of γ-butyrolactone were added thereto. Stir until. Next, 10 g of pentanediol bis-trim anhydride ester was added, and the mixture was stirred for 1 hour while cooling with ice, and then at room temperature for 6 hours. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (ii) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (ii), solid content of the solution of the polyimide precursor (ii), and a weight average molecular weight are shown in Table 1.

Synthesis Example 3 Synthesis of Polyimide Precursor (iii)

Into a three-neck separable flask, 9.7 g of 1,3-bis (3-aminophenoxy) benzene, 13.7 g of polytetramethylene oxide-di-p-aminobenzoate and 168.8 g of γ-butyrolactone were added. Stir until. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (iii) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (iii), solid content of the solution of the polyimide precursor (iii), and a weight average molecular weight are shown in Table 1.

Synthesis Example 4 Synthesis of Polyimide Precursor (iv)

Into a three-neck separable flask, 8.8 g of 1,3-bis (3-aminophenoxy) benzene, 12.4 g of polytetramethylene oxide-di-p-aminobenzoate, and 99.7 g of γ-butyrolactone were added. Stir until. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (iv) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (iv), solid content of the polyimide precursor (iv) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 5 Synthesis of Polyimide Precursor (v)

Into a three-neck separable flask, 10.0 g of trimethylene-bis (4-aminobenzoate), 13.1 g of polytetramethylene oxide-di-p-aminobenzoate and 104.1 g of γ-butyrolactone were added to obtain a homogeneous solution. Stir until. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (v) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (v), solid content of the polyimide precursor (v) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 6 Synthesis of Polyimide Precursor (vi)

Into a three-neck separable flask, 9.8 g of trimethylene-bis (4-aminobenzoate), 12.9 g of polytetramethylene oxide-di-p-aminobenzoate, and 103.1 g of γ-butyrolactone were added to form a homogeneous solution. Stir until. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (vi) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (vi), solid content of the solution of the polyimide precursor (vi), and a weight average molecular weight are shown in Table 1.

Synthesis Example 7 Synthesis of Polyimide Precursor (vii)

Into a three-neck separable flask, 9.5 g of trimethylene-bis (4-aminobenzoate), 12.4 g of polytetramethylene oxide-di-p-aminobenzoate, and 101.0 g of γ-butyrolactone were added to obtain a homogeneous solution. Stir until. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (vii) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (vii), solid content of the solution of the polyimide precursor (vii), and a weight average molecular weight are shown in Table 1.

Synthesis Example 8 Synthesis of Polyimide Precursor (viii)

Into a three-neck separable flask, 9.1 g of trimethylene-bis (4-aminobenzoate), 15.4 g of polytetramethylene oxide-di-p-aminobenzoate, and 107.3 g of γ-butyrolactone were added to obtain a homogeneous solution. Stir until. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (viii) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (viii), solid content of the solution of the polyimide precursor (viii), and a weight average molecular weight are shown in Table 1.

Synthesis Example 9 Synthesis of Polyimide Precursor (ix)

Into a three-neck separable flask, 9.8 g of trimethylene-bis (3-aminobenzoate), 12.9 g of polytetramethylene oxide-di-p-aminobenzoate, and 103.1 g of γ-butyrolactone were added to form a homogeneous solution. Stir until. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (ix) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (ix), solid content of the polyimide precursor (ix) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 10 Synthesis of Polyimide Precursor (x)

9.8 g of trimethylene-bis (4-aminobenzoate), 12.9 g of poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate) in a three-neck separable flask, 103.1 g was added and stirred until it became a homogeneous solution. Next, 10 g of pentanediol-bis-trimellinate anhydride and 11.5 g of decanediol-bis-trimellitate anhydride were added, and it stirred at room temperature for 1 hour, and 6 hours after cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (x) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (x), solid content of the polyimide precursor (x) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 11 Synthesis of Polyimide Precursor (xi)

Into a three-neck separable flask, 10.1 g of trimethylene-bis (4-aminobenzoate), 13.3 g of polytetramethylene oxide-di-p-aminobenzoate, and 105.7 g of γ-butyrolactone were added to form a homogeneous solution. Stir until. Next, 10 g of butanediol-bis-trim anhydride esters and 11.9 g of decandiol-bis-trim anhydride ester were added, and the mixture was stirred for 1 hour while cooling with ice, and then at room temperature for 6 hours. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (xi) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xi), solid content of the polyimide precursor (xi) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 12 Synthesis of Polyimide Precursor (xii)

Into a three-neck separable flask, 9.8 g of trimethylene-bis (4-aminobenzoate), 12.9 g of polytetramethylene oxide-di-p-aminobenzoate, and 110.4 g of γ-butyrolactone were added to obtain a homogeneous solution. Stir until. Next, 10 g of pentanediol-bis-trim anhydride esters and 14.6 g of dioxane-bis-trim anhydride ester were added, and the mixture was stirred for 1 hour while cooling with ice, and then at room temperature for 6 hours. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (xii) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xii), solid content of the polyimide precursor (xii) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 13 Synthesis of Polyimide Precursor (xiii)

Into a three-neck separable flask, 9.8 g of trimethylene-bis (4-aminobenzoate), 12.9 g of polytetramethylene oxide-di-p-aminobenzoate, and 123.9 g of γ-butyrolactone were added to form a homogeneous solution. Stir until. Next, 10 g of pentanediol-bis-trim anhydride esters and 20.4 g of polypropylenediol-bis-trim anhydride esters were added, and the mixture was stirred for 1 hour while cooling with ice, and then at room temperature for 6 hours. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (xiii) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xiii), the solid content of the polyimide precursor (xiii) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 14 Synthesis of Polyimide Precursor (xiv)

Into a three-neck separable flask, 9.4 g of 1,3-bis (3-aminophenoxy) benzene and 73 g of γ-butyrolactone were added and stirred until a homogeneous solution was obtained. Next, 10 g of 4,4'- oxydiphthalic acid dianhydrides were added, and it stirred for 1 hour, and 6 hours at room temperature, ice-cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (xiv) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xiv), solid content of the polyimide precursor (xiv) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 15 Synthesis of Polyimide Precursor (xv)

7.1 g of 1, 3-bis (3-aminophenoxy) benzene and 64.3 g of (gamma) -butyrolactone were put into the three neck separable flask, and it stirred until it became a homogeneous solution. Next, 10 g of ethylenediol-bis- trimellitic acid ester was added, and it stirred for 1 hour, and 6 hours at room temperature, ice-cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (xv) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xv), the solid content of the polyimide precursor (xv) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 16 Synthesis of Polyimide Precursor (xvi)

Into a three-neck separable flask, 2.7 g of 1,3-bis (3-aminophenoxy) benzene, 26.3 g of polytetramethylene oxide-di-p-aminobenzoate, and 91.0 g of γ-butyrolactone were added. Stir until. Next, 10 g of 4,4'- oxydiphthalic acid dianhydrides were added, and it stirred for 1 hour, and 6 hours at room temperature, ice-cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (xvi) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xvi), the solid content of the polyimide precursor (xvi) solution, and a weight average molecular weight are shown in Table 1.

Synthesis Example 17 Synthesis of Polyimide Precursor (xvii)

2.0 g of 1,3-bis (3-aminophenoxy) benzene, 19.9 g of polytetramethylene oxide-di-p-aminobenzoate, and 74.4 g of γ-butyrolactone were added to a three-neck separable flask. Stir until. Next, 10 g of ethylenediol-bis- trimellitic acid ester was added, and it stirred for 1 hour, and 6 hours at room temperature, ice-cooling. Next, the product was filtered under pressure with the filter of 5 micrometers, and the polyimide precursor (xvii) was obtained. The molar ratio of the acid dianhydride and diamine of the obtained polyimide precursor (xvii), the solid content of the polyimide precursor (xvii) solution, and a weight average molecular weight are shown in Table 1.

(Combination of Photosensitive Polyimide Precursor Composition)

First, a predetermined amount of polyimide precursor is divided into containers such as glass bottles. Next, a predetermined amount of additives such as a photosensitizer or a dissolution inhibiting agent is blended and stirred until uniform with a mix rotor or the like. By these operations, the photosensitive polyimide precursor composition can be obtained.

(Measurement of Weight Average Molecular Weight)

1: Measurement of the weight average molecular weight of the polyimide precursor

0.01 g of the synthesized polyimide precursor was measured by precision balance, and dissolved in 10 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). The solution was passed through a 10 μm filter to filter, and the molecular weight was measured by gel permeation chromatography (manufactured by Nippon Spectroscopy) equipped with TSK-GEL SUPER HM-H (trade name manufactured by Tosoh Corporation).

2: Measurement of the weight average molecular weight of the photosensitive polyimide precursor composition

Application | coating: The polyester film was affixed by mounting a polyester film (made by Unichika Co., Ltd.) on the coating table (made by Matsuki Scientific Co., Ltd.) which can be vacuum-sorption and heated, and vacuum-adsorption. On this polyester film, the photosensitive polyimide precursor composition was apply | coated using the applicator (made by Matsuki Scientific) whose gap is 67.5 micrometers.

Desolvent: The desolvent was performed on the conditions of 30 minutes at 95 degreeC with the dryer (SPH-201, the product made by ESPEC Co., Ltd.).

Molecular weight measurement: 0.01 g of the photosensitive polyimide precursor composition obtained after the solvent removal was measured by precise balance, and dissolved in 10 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). The solution was passed through a 10 μm filter to filter, and the molecular weight was measured by gel permeation chromatography (manufactured by Nippon Spectroscopy) equipped with TSK-GEL SUPER HM-H (trade name manufactured by Tosoh Corporation).

Calculation of molecular weight ratio: When the weight average molecular weight M1 of the photosensitive polyimide precursor composition varnish and the weight average molecular weight M2 of the said photosensitive polyimide precursor composition after a solvent were made, the molecular weight ratio was computed by the following formula (1).

Molecular weight ratio = M2 / M1

(Bending test)

Coating: The polyester film was affixed by mounting a polyester film (manufactured by Unichika Co., Ltd.) on a coating table (manufactured by Matsuki Scientific Co., Ltd.) capable of vacuum adsorption and heating and vacuum adsorption. On this polyester film, the photosensitive polyimide precursor composition was apply | coated using the applicator (made by Matsuki Scientific) whose gap is 100 micrometers.

Desolvent: The desolvent was performed on the conditions of 30 minutes at 95 degreeC with the dryer (SPH-201, the product made by ESPEC Co., Ltd.).

Bending test: The film obtained after the desolvent was bent 180 degrees (wrinkling bent), and cracking and peeling of the photosensitive layer were visually observed. (Circle) and the case where there exists a crack and peeling were made into the case where there was no crack and peeling.

(Bending evaluation)

Coating: The polyester film was affixed by mounting a polyester film (manufactured by Unichika Co., Ltd.) on a coating table (manufactured by Matsuki Scientific Co., Ltd.) capable of vacuum adsorption and heating and vacuum adsorption. On this polyester film, the photosensitive polyimide precursor composition was apply | coated using the applicator (made by Matsuki Scientific) whose gap is 67.5 micrometers.

Desolvent: The desolvent was performed on the conditions of 30 minutes at 95 degreeC with the dryer (SPH-201, the product made by ESPEC).

Vacuum press: The photosensitive dry film obtained by the desolvent process by the vacuum press machine (made by SA-501 tester industry company) using the polyimide film (made by Kapton EN-100 brand Toray DuPont) for a base material is press temperature 100 degreeC The vacuum press was performed on the conditions of the press pressure of 0.5 Mpa, the vacuum degree of 15 Pa, and the press time 1 minute.

Bake: Curing was carried out under the conditions shown in Table 5 using a dryer (manufactured by SPH-201 Espek Co., Ltd.).

Measurement of warpage: The film obtained after baking was cut out to 5 cm in length and 5 cm in width, and the warpage of the film was measured using a ruler after removing static electricity.

(Example 1)

Evaluation of the photosensitive polyimide precursor composition which consists of a polyimide precursor and a photosensitive agent

10 g of the polyimide precursor solution obtained in Synthesis Examples 1 to 3 and 0.42 g of 20 parts by mass of the quinonediazide compound (Formula 16) were mixed with the polyimide precursor solid as a photosensitive agent in a ratio of 20 to a glass bottle. It stirred until it became uniform by the mix rotor (made by MR-5 Azwan company), and obtained the photosensitive polyimide precursor composition (1-3). Table 2 shows the results of the evaluation.

(23)

(Example 2)

Evaluation of the photosensitive polyimide precursor composition using 3'-hydroxyacetanilide as a dissolution inhibitor

10 g of the polyimide precursor solution obtained in Synthesis Examples 1 to 3, 0.42 g of 20 parts by mass of the quinonediazide compound (Formula 16) with respect to the polyimide precursor solids as the photosensitizer, and 12.5 parts by mass of 3'-hydroxyacetic acid with respect to the polyimide precursor 0.26 g of anilide was mixed in the ratio shown in Table 3, it put into the 20 kPa glass bottle, and it stirred until it became uniform by the mix rotor (MR-5 Azwan company make), and obtained the photosensitive polyimide precursor composition (4-6). Table 3 shows the results of the evaluation.

(Example 3)

Evaluation of the Photosensitive Polyimide Precursor Composition Using a Phenolic Compound

10 parts by mass of the polyimide precursor solution obtained in Synthesis Examples 1 to 3, 0.42 g of the quinonediazide compound represented by the above general formula (16) based on 20 parts by mass of the polyimide precursor solid as the photosensitizer, and 20 parts by mass of the following general 0.42 g of the phenolic compound represented by the formula (17) was mixed in the ratio shown in Table 4, placed in a 20 kPa glass bottle, stirred until uniform by a mixing rotor (manufactured by MR-5 Azwan Corporation), and the photosensitive polyimide precursor composition ( 7 to 9) was obtained. The evaluation results are shown in Table 4.

[Formula 24]

(Comparative Example 1)

Photosensitive polyimide precursor compositions (10 to 11) shown in Table 2 were obtained in the same manner as in Example 1 except that 10 g of the polyimide precursor solution obtained in Synthesis Examples 14 to 15 was used. Table 2 shows the results of the evaluation.

(Comparative Example 2)

Photosensitive polyimide precursor compositions (12 to 13) shown in Table 3 were obtained in the same manner as in Example 2, except that 10 g of the polyimide precursor solution obtained in Synthesis Examples 14 to 15 was used. Table 3 shows the results of the evaluation.

(Comparative Example 3)

Photosensitive polyimide precursor compositions (14 to 15) shown in Table 4 were obtained in the same manner as in Example 3, except that 10 g of the polyimide precursor solution obtained in Synthesis Examples 14 to 15 was used. The evaluation results are shown in Table 4.

When using the photosensitive polyimide precursor composition for the cover film of a flexible printed wiring board, etc., it is necessary to obtain a desired pattern by lithography in the developing solution which consists of aqueous alkali solution. In addition to the fact that the molecular weight of the composition does not change over time, the tackiness is excellent, the laminate laminated with the cover film after baking is not bent, the peeling and cracking does not occur even if it is bent, and the laminate is burnt. Performance is required.

(Performance Evaluation of Photosensitive Polyimide Precursor Composition)

1) Evaluation of Material Stability

Coating: The polyester film was affixed by mounting a polyester film (manufactured by Unichika Co., Ltd.) on a coating table (manufactured by Matsuki Scientific Co., Ltd.) capable of vacuum adsorption and heating and vacuum adsorption. On this polyester film, the photosensitive polyimide precursor composition was apply | coated using the applicator (made by Matsuki Scientific) whose gap is 67.5 micrometers.

Desolvent: The desolvent was performed on the conditions of 30 minutes at 95 degreeC with the dryer (SPH-201, the product made by ESPEC Co., Ltd.).

Molecular weight measurement: 0.01 g of the photosensitive polyimide precursor composition obtained after the solvent removal was measured by precise balance, and dissolved in 10 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). The solution was passed through a 10 μm filter to filter, and the molecular weight was measured by gel permeation chromatography (manufactured by Nippon Spectroscopy) equipped with TSK-GEL SUPER HM-H (trade name manufactured by Tosoh Corporation).

Calculation of molecular weight ratio: When the weight average molecular weight M1 of the photosensitive polyimide precursor composition varnish and the weight average molecular weight M2 of the said photosensitive polyimide precursor composition after a solvent were made, the molecular weight ratio was computed by the following formula (1).

Molecular weight ratio = M2 / M1

2: lithography performance evaluation

Coating: The polyester film was affixed by mounting a polyester film (manufactured by Unichika Co., Ltd.) on a coating table (manufactured by Matsuki Scientific Co., Ltd.) capable of vacuum adsorption and heating and vacuum adsorption. On this polyester film, the photosensitive polyimide precursor composition was apply | coated using the applicator (made by Matsuki Scientific) whose gap is 67.5 micrometers.

Desolvent: The desolvent was performed on the conditions of 30 minutes at 95 degreeC with the dryer (SPH-201, the product made by ESPEC).

Vacuum press: The FCCL was first washed with 15 wt% aqueous sodium persulfate solution. Next, a vacuum press was performed on the photosensitive dry film obtained by the desolvent process by the vacuum press machine (SA-501 tester industry make) on the conditions of press temperature of 100 degreeC, press pressure of 0.5 Mpa, vacuum degree of 15 Pa, and press time of 1 minute. .

Active light irradiation: The support film of the laminated body obtained by the vacuum press process was peeled, and the ultraviolet-ray was irradiated on the conditions of exposure amount 1.5 J / cm <2> using the ultrahigh pressure mercury lamp (made by HMW-201KB Oak company).

Lithography: Time until the UV irradiation part is completely dissolved under the conditions of a developing temperature of 30 ° C. and a spray pressure of 0.18 MPa using a 1 wt% aqueous sodium carbonate solution in a developer by a spray type developer (hereinafter referred to as break point). Was measured. Next, development was performed at a developing time 1.2 times that of the break point. After the development, washing with distilled water for developing time x 1/3 was carried out with a spray washer, followed by further washing for 30 seconds with an aqueous 0.2 wt% sulfuric acid solution.

Lithography Performance: Lithography performance was judged by development time, residual film rate, and pattern shape.

Developing time: (circle) and the photosensitive polyimide precursor composition which exceeded 90 second for the photosensitive polyimide precursor composition whose developing time is 90 second or less were described with x.

Residual film ratio measurement: The film thickness of the photosensitive layer before image development was computed by the following formula | equation, making T1 and the film thickness of the photosensitive layer after image development T2.

Residual rate = T2 / T1 × 100 (%)

Pattern shape: The pattern after lithography observed the shape of the 100 micrometer circle pattern on the light visual field and the conditions of 100 times using the optical microscope (made by ECLIPS LV100 Nikon Corporation). (Circle) and the thing which fell apart that hold | maintained the shape of a pattern were described with x.

3: Tackiness Evaluation of Photosensitive Dry Film

Coating: The polyester film was affixed by mounting a polyester film (manufactured by Unichika Co., Ltd.) on a coating table (manufactured by Matsuki Scientific Co., Ltd.) capable of vacuum adsorption and heating and vacuum adsorption. On this polyester film, the photosensitive polyimide precursor composition was apply | coated using the applicator (made by Matsuki Scientific) whose gap is 67.5 micrometers.

Desolvent: The desolvent was performed on the conditions of 30 minutes at 95 degreeC with the dryer (SPH-201, the product made by ESPEC).

Tackiness evaluation: The presence or absence of the tack of the photosensitive layer after a desolvent was evaluated by acceleration (vi). The thing with a fingerprint and x and the thing with no fingerprint were described as (circle).

4: resistance evaluation

Cure: After lithography, a cure was performed under the conditions shown in Table 5 using a dryer (manufactured by SPH-201 Espek Co., Ltd.).

Bending test: The film obtained after curing was bent at 180 degrees (wrinkling bend), and cracking and peeling of the cover film were visually observed. (Circle) and the case where there exists a crack and peeling were made into the case where there was no crack and peeling.

5: warpage evaluation

Coating: The polyester film was affixed by mounting a polyester film (manufactured by Unichika Co., Ltd.) on a coating table (manufactured by Matsuki Scientific Co., Ltd.) capable of vacuum adsorption and heating and vacuum adsorption. On this polyester film, the photosensitive polyimide precursor composition was apply | coated using the applicator (made by Matsuki Scientific) whose gap is 67.5 micrometers.

Desolvent: The desolvent was performed on the conditions of 30 minutes at 95 degreeC with the dryer (SPH-201, the product made by ESPEC).

Vacuum press: The photosensitive dry film obtained by the desolvent process by the vacuum press machine (made by SA-501 tester industry company) using the polyimide film (made by Kapton EN-100 brand Toray DuPont) for a base material is press temperature 100 degreeC The vacuum press was performed on the conditions of the press pressure of 0.5 Mpa, the vacuum degree of 15 Pa, and a press time of 1 minute.

Bake: Curing was carried out under the conditions shown in Table 5 using a dryer (manufactured by SPH-201 Espek Co., Ltd.).

Measurement of warpage: The film obtained after baking was cut out to 5 cm in length and 5 cm in width, and the warpage of the film was measured using a ruler after removing static electricity.

6: flame retardancy evaluation

Application | coating and the removal solvent were performed similarly to evaluation of curvature.

Vacuum press: The photosensitive dry film obtained by the desolvent process by the vacuum press machine (made by SA-501 tester industry company) using the polyimide film (made by Kapton EN-100 brand Toray DuPont) for a base material is press temperature 100 degreeC. The vacuum press was performed on both surfaces of the polyimide film on the conditions of the press pressure of 0.5 Mpa, the vacuum degree of 15 Pa, and a press time of 1 minute.

Bake: Curing was carried out under the conditions shown in Table 5 using a dryer (manufactured by SPH-201 Espek Co., Ltd.).

Flame retardancy test: The film obtained by the baking process was cut out to 1 cm in width and 5 cm in length. Next, one end of the test piece was set on fire and the fire spread and the burning process was visually observed. (Circle) and the sample which burnt out the sample which turned off the fire on the way were made into x.

(Example 4 to Example 22)

To 10 g of the polyimide precursor solution obtained in Synthesis Example 2 to Synthesis Example 13, various additives were mixed at the ratios shown in Table 6-1, placed in a 20 kPa glass bottle, and mixed with a rotor (manufactured by MR-5 Azwan Corporation). It stirred until it became uniform by and obtained the photosensitive polyimide precursor composition (16-34). The evaluation results of these photosensitive polyimide precursor compositions are shown in Table 7-1.

(Comparative Example 4-Comparative Example 7)

To 10 g of the polyimide precursor solution obtained in Synthesis Example 16 to Synthesis Example 17, various additives were mixed at the ratio shown in Table 6-2, placed in a 20 kPa glass bottle, and mixed with a rotor (manufactured by MR-5 Azwan). It stirred until it became uniform by and obtained the photosensitive polyimide precursor composition (35-38). The evaluation results of these photosensitive polyimide precursor compositions are shown in Table 7-2.

In addition, in Example 4-Example 22 and Comparative Examples 4-7, the compound of following formula (18)-formula (27) was used as an additive.

Dissolution Inhibitors 1

[Formula 25]

Melt Inhibitor 2

[Formula 26]

[Formula 27]

[Formula 28]

Flame retardant

[Formula 29]

[Formula 30]

[Formula 31]

Thermal base generator

[Formula 32]

[Formula 33]

[Formula 34]

TABLE 1

TABLE 2

[Table 3]

[Table 4]

TABLE 5

Table 6-1

Table 6-2

Table 7-1

Table 7-2

As shown in Table 2-Table 4, Example 1-Example 3 using the polyimide precursor which concerns on this invention have shown that there is no fall (M2 / M1) of molecular weight. Moreover, the wrinkle bending strength was also favorable. This result is considered to be because the decomposition of the polyimide precursor at the time of the desolvent was suppressed, and the molecular weight fall was suppressed by using the acid dianhydride which concerns on this invention. On the other hand, in Comparative Examples 1 to 3 using other acid dianhydrides, it is found that while the molecular weight is lowered, the wrinkle bending strength is lowered.

Moreover, as shown in Table 7-1 and Table 7-2, Example 4-Example 22 using the polyimide precursor composition which concerns on this invention show that a residual film rate is favorable. In particular, in Example 8, the residual film ratio is 90% without adding the dissolution inhibiting agent. These results are considered to be because decomposition of the polyimide precursor in the image development process was suppressed by using the acid dianhydride which concerns on this invention. Example 4-Example 22 show that tackiness is also favorable. On the other hand, under any conditions using other acid dianhydrides, the residual film rate is lowered, indicating that the tackiness is inferior.

The polyimide precursor of the present invention can be suitably used as a surface protective film, an interlayer insulating film, and a redistribution insulating film of a semiconductor device, a protective film of a device having a bump structure, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper plate, and a liquid crystal alignment film. Can be.

Claims (12)

An acid dianhydride represented by the following general formula (1) is contained, The polyimide precursor characterized by the above-mentioned.
[Formula 1]

(X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms. R ₁ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.) The method of claim 1,
Said polyimide precursor contains the diamine represented by following General formula (2), The polyimide precursor characterized by the above-mentioned.
(2)

(Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. R ₂ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group.) The method according to claim 1 or 2,
The said polyimide precursor contains the acid dianhydride represented by following General formula (3), The polyimide precursor characterized by the above-mentioned.
(3)

(a represents an integer of 1 to 20. b represents an integer of 3 to 30. R ₃ represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms) The method according to claim 1 or 2,
The said polyimide precursor contains the diamine represented by following General formula (4), The polyimide precursor characterized by the above-mentioned.
[Chemical Formula 4]

(Z is an alkylene group having 2 to 20 carbon atoms. R ₄ represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group. C represents an integer of 2 to 30.) The method of claim 2,
The said polyimide precursor contains the acid dianhydride represented by following General formula (3), The polyimide precursor characterized by the above-mentioned.
[Chemical Formula 5]

(a represents an integer of 1 to 15. b represents an integer of 5 to 20. R ₃ represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms) The method of claim 4, wherein
The diamine represented by the said General formula (4) is 25 mol%-75 mol% in all the diamine components, The polyimide precursor characterized by the above-mentioned. 100 mass parts of polyimide precursors as described in any one of Claim 1, 2, or 5, and 5 mass parts-35 mass parts of photosensitizers, The photosensitive polyimide precursor composition characterized by the above-mentioned. The method of claim 7, wherein
The photosensitive polyimide precursor composition, wherein the photosensitive agent contains a quinonediazide structure. The method of claim 7, wherein
A photosensitive polyimide precursor composition comprising a dissolution inhibiting agent having a phenolic hydroxyl group. The photosensitive dry film obtained by apply | coating the photosensitive polyimide precursor composition of any one of Claims 7-9 to a support film, desolvent, and then laminating | stacking a cover film. It formed using the photosensitive dry film of Claim 10, The flexible printed wiring board characterized by the above-mentioned. The ratio (Mw2 / Mw1) between the weight average molecular weight (Mw1) in a varnish and the weight average molecular weight (Mw2) after desolvent at 120 degrees C or less is 0.7 or more, The polyimide precursor characterized by the above-mentioned.