TWI384015B - A polyimide precursor, a photosensitive polyimide precursor composition, a photosensitive dry film, and a flexible printed circuit board using the same - Google Patents

Description

Polyimine precursor, photosensitive polyimide precursor composition, photosensitive dry film, and flexible printed circuit board using the same

The present invention relates to a polyimide precursor, a photosensitive polyimide precursor composition, a photosensitive dry film, and a flexible printed circuit board using the same.

In recent years, a film-shaped printed circuit board called a flexible printed circuit board (hereinafter also referred to as "FPC (Flexible Printed Circuit)") has prospered. The substrate is formed on a FCCL (Flexible Cupper Clad Laminate) having a wiring layer formed of a polyimide film or the like, and is mainly used for a mobile phone, a notebook computer, a digital camera, and the like. . Since the FPC maintains its function even when it is bent, it is an indispensable material for miniaturization and weight reduction of equipment. In particular, in recent years, electronic devices represented by notebook computers have been developed to be smaller and lighter, and FPCs have been used in such products to contribute to reduction in size and weight of related devices, reduction in product cost, and design simplification. .

The coating layer provided in the FPC is mainly formed by bonding using a polyimide film having an adhesive or the like. However, due to the miniaturization and thinning of the FPC, the positional accuracy of the bonding is problematic. Therefore, development of a photosensitive coating layer capable of performing high-precision microfabrication only on a necessary portion by irradiation with active light such as ultraviolet rays has begun. Among them, the dry film type photosensitive cover layer exhibits excellent dimensional accuracy and does not require a solvent drying step. Therefore, when manufacturing an FPC, the process can be simplified, and it is expected to be a material having a low environmental load.

Among the photosensitive cover materials, the photosensitive cover layer of the polyimide precursor is used as an excellent cover layer from the viewpoint of bending resistance, heat resistance and electrical insulation derived from polyimide. . For example, Patent Document 1 discloses a heat-resistant adhesive using tetracarboxylic dianhydride and a diamine. Further, Patent Document 2 discloses that a photosensitive photosensitive heat-resistant resin composition is formed using a film of a polyimide precursor, and Patent Document 3 discloses a photosensitive top coating material containing polyamic acid. Further, Patent Document 4 discloses an adhesive film containing a specific acid dianhydride. However, in the case of using a photosensitive cover layer of a polyimide precursor, a problem of stickiness of the photosensitive dry film or a solvent removal due to the formation of the photosensitive dry film may occur. The molecular weight of the precursor is lowered, and the obtained photosensitive dry film is bent to cause a problem of cracking of the photosensitive layer. Further, since the molecular weight of the polyimide precursor is lowered, when the pattern is formed by the lithography, the development time is unstable in the development using the alkaline aqueous solution, the film thickness of the pattern is reduced, and the shape of the pattern is deformed. Further, in the step of converting the polyimine precursor into a polyimine, the stress caused by the ring closure reaction accompanying the desolvation or the sulfhydryl imidization of the polyimide precursor may cause warping in the FPC. song. If warpage occurs in the FPC, there is a problem that the adhesion between the FCCL and the cover layer is poor, or the driving power of the electronic device having the FPC is high. Therefore, it is sought to improve the warpage of the FPC having a coating layer on the copper wiring.

In addition, the cover layer was sought to exhibit flame retardancy in the flame retardancy test represented by the UL specification VTM test. The halogen compound is formulated in the original cover layer for the purpose of exhibiting flame retardancy. However, from the viewpoint of environmental protection or biotoxicity, it is desirable to exhibit flame retardancy in a non-halogen.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-269622

[Patent Document 2] Japanese Patent Laid-Open No. 04-18450

[Patent Document 3] Japanese Patent Laid-Open No. Hei 05-158237

[Patent Document 4] Japanese Patent Laid-Open No. Hei 10-330723

The present invention has been developed in view of the above-described aspects, and an object thereof is to provide a polyimine precursor which is less warp and has excellent bendability after baking, and is used in the case of FPC. An imide precursor composition, a photosensitive dry film, and a flexible printed circuit board using the same.

The polyimine precursor of the present invention is characterized by comprising an acid dianhydride represented by the following formula (1).

[Chemical 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 polyimine precursor of the present invention preferably contains a diamine represented by the following formula (2).

[Chemical 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 polyimine precursor of the present invention preferably contains an acid dianhydride represented by the following formula (3).

[Chemical 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 a carbon number of 1 to 10)

The polyimine precursor of the present invention preferably contains a diamine represented by the following formula (4).

[Chemical 4]

(Z is a stretching alkyl 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 polyimine precursor of the present invention preferably contains an acid dianhydride represented by the following formula (3).

[Chemical 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 a carbon number of 1 to 10)

In the polyimine precursor of the present invention, it is preferred that the diamine represented by the above formula (4) is from 25 mol% to 75 mol% in all the diamine components.

The photosensitive polyimide intermediate precursor composition of the present invention contains 100 parts by mass of the above polyimide precursor and 5 to 30 parts by mass of a sensitizer.

In the photosensitive polyimine precursor composition of the present invention, it is preferred that the sensitizer contains a quinonediazide structure.

In the photosensitive polyimine precursor composition of the present invention, a compound having a phenolic hydroxyl group is preferably contained as a dissolution inhibitor.

The photosensitive dry film of the present invention is characterized in that the photosensitive polyimide intermediate precursor composition is applied onto a support film, and a solvent is removed, followed by lamination of the cover film.

The flexible printed circuit board of the present invention is characterized in that it is formed using the above-described photosensitive dry film.

The polyimine precursor of the present invention is characterized in that the ratio (Mw2/Mw1) between the weight average molecular weight (Mw1) of the varnish and the weight average molecular weight (Mw2) after desolvation of 120 ° C or less is 0.7 or more.

The photosensitive polyimide intermediate precursor composition of the present invention achieves a low warpage of FPC after baking by using a polyimide intermediate precursor obtained from an acid dianhydride having a specific structure. And the effect of excellent bending property.

Hereinafter, the present invention will be specifically described.

(A) Polyimine precursor

The single system of the polyimide precursor uses acid dianhydride and diamine. It is known that the molecular weight of the polyimine precursor is lowered by the solvent to be removed by heating, and the acid dianhydride used for the polyimide precursor is used by the following formula (1) from the viewpoint of decreasing the molecular weight. Said acid dianhydride. The acid dianhydride represented by this structure may be used alone or in combination of two or more. By suppressing a decrease in the molecular weight in the solvent removal step, it is possible to prevent breakage at the time of bending when the photosensitive dry film is formed, and to improve the bendability.

[Chemical 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, from the viewpoint of suppressing a decrease in the molecular weight in the solvent removal step, it is preferred to use an acid dianhydride represented by the following formula (3).

[Chemistry 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 a carbon number of 1 to 10)

In the acid dianhydride represented by the above formula (3), a is preferably from 1 to 15, and b is preferably from 5 to 20. Specific examples thereof include butanediol-bis-p-trimellitic anhydride, pentanediol-bis-p-trimellitic anhydride, heptanediol-bis-p-trimellitic anhydride, decanediol-bis-p-trimellitic anhydride, Eicosanediol-bis-p-trimellitic anhydride, polypropylene glycol-trimellitic anhydride, polytetramethylene glycol-bis-p-trimellitic anhydride, and the like. These compounds may be used singly or in combination of two or more.

In the polyimine precursor of the present invention, in addition to the above acid dianhydride, other acid dianhydride may be used. Specifically, examples of the aromatic tetracarboxylic acid include pyromellitic dianhydride, 3,3′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3′,4′-biphenyl. Tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3' - benzophenone tetracarboxylic 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 Dihydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 3,3'-oxydiphthalic dianhydride, 4,4 '-Oxydiphthalic dianhydride, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-dihydro-1,3-dioxo-5-iso Benzofurancarboxylic acid-1,4-phenylenedicarboxylate, 4-(2,5-dioxotetrahydrofuran-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-anthracene Tetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy) Hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane dianhydride, 2,2'-bis(trifluoromethyl) -4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, ethylene glycol-p-trimellitic anhydride ester, and the like.

Examples of the aliphatic tetracarboxylic dianhydride include cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and 2,3,5,6-cyclohexanetetracarboxylic acid Anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo[2,2,2]octyl- 7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride. From the viewpoint of reducing the warpage after baking, the total amount of the acid dianhydride relative to the polydiimide precursor is preferably from 0 mol% to 50 mol%. .

As a diamine used for the polyimide precursor, it is preferable to use the lower side from the viewpoint of suppressing the molecular weight in the solvent removal step and the viscosity improvement after the solvent is removed to form a photosensitive dry film. The diamine represented by the formula (2). The diamines represented by the above structures may be used singly or in combination of two or more. In the following general formula (2), R _{2 is} preferably a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms.

[化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)

Specific examples thereof include bis(2-aminobenzoic acid) ethylene glycol ester, bis(3-aminobenzoic acid) ethylene glycol ester, bis(4-aminobenzoic acid) ethylene glycol ester, and bis(2-amine). Benzoic acid) 1,3-propane diester, bis(3-aminobenzoic acid) 1,3-propane diester, bis(4-aminobenzoic acid) 1,3-propane diester, bis(2- Aminobenzoic acid) 1,4-butane diester, bis(3-aminobenzoic acid) 1,4-butane diester, bis(4-aminobenzoic acid) 1,4-butane diester, double (2 -aminobenzoic acid) 3-methyl-1,4-butane diester, bis(3-aminobenzoic acid) 3-methyl-1,4-butane diester, bis(4-aminobenzoic acid) 3-methyl-1,4-butane diester, bis(2-aminobenzoic acid) 1,5-pentane diester, bis(3-aminobenzoic acid) 1,5-pentane diester, bis (4) -aminobenzoic acid) 1,5-pentane diester, bis(2-aminobenzoic acid) 1,10-decane diester, bis(3-aminobenzoic acid) 1,10-decane diester, bis ( 4-aminobenzoic acid) 1,10-decane diester, and the like. These diamines may be used singly or in combination of two or more kinds.

Furthermore, it is preferable to use the following formula (4) from the viewpoint of suppressing the molecular weight drop in the solvent removal step and improving the viscosity when the photosensitive dry film is formed after solvent removal. Compound.

[Chemistry 9]

(Z is a stretching alkyl 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)

Specific examples thereof include polyoxymethylene-di-o-amino benzoate, polyoxymethylene-di-m-amino benzoate, polyoxymethylene-di-pair. Amino benzoate, polyoxymethylene-di-o-amino benzoate, polyoxymethylene-di-m-amino benzoate, polyoxymethylene-di-p-amino group Benzoate, polyoxytetramethylene-di-o-amino benzoate, polyoxytetramethylene-di-m-amino benzoate, polyoxytetramethylene-di-p-amine Benzoate, polyoxy-3-methyltetramethylene-di-o-amino benzoate, polyoxy-3-methyltetramethylene-di-m-amino benzoate, polyoxidation 3-methyltetramethylene-di-p-amino benzoate, polyoxypentaethylene-di-o-amino benzoate, polyoxypentaethylene-di-m-aminobenzamide Acid ester, polyoxypentamethyl-di-p-amino benzoate, polyoxymethylene-di-o-amino benzoate, polyoxymethylene-di-m-amino benzene Formate, polyoxymethylene-di-p-aminobenzoate, poly(tetramethylene/3-methyltetramethylene ether) glycol double (4 -Aminobenzoic acid ester) and the like. These diamines may be used singly or in combination of two or more kinds.

Further, from the viewpoint of reducing the warpage after baking, the amount of the diamines is preferably such that the diamine represented by the above formula (4) is 25 mol% to all the diamine components. 75 moles %.

Particularly preferably, the compound represented by the above formula (2) is used together with the compound represented by the above formula (4). When the compound represented by the above formula (2) is used together with the compound represented by the above formula (4), the viscosity at the time of forming a photosensitive dry film is improved by reducing warpage and solvent removal, From the viewpoint of good lithographic characteristics, the compounding amount of the compound represented by the above formula (4) is preferably from 25 mol% to 75 mol% based on the total amount of the diamine.

Further, the above diamine may be used together with a diamine other than the above. Specific examples thereof include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4' -diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,7-diamino-dimethylbenzothiophene-5 , 5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis(4-aminophenyl) sulfide, 4,4'-Diaminodiphenylphosphonium, 4,4'-diaminobenzimidamide, 1,n-bis(4-aminophenoxy)alkane, 1,3-bis(4- Aminophenoxy)-2,2-dimethylpropane, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-amino group Phenyl)indole, 5(6)-amino-1-(4-aminomethyl)-1,3,3-trimethylindan, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) Benzene, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis(4-aminophenoxyphenyl)propane, bis[4-(4-aminophenoxy) Phenyl]indole, bis[4-(3-aminophenoxy)phenyl]indole 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 4,6-di Hydroxy-1,3-phenylenediamine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 1,4-bis(4-aminophenoxy)pentane, 1,5- Bis(4'-aminophenoxy)pentane, bis(γ-aminopropyl)tetramethyldioxane, 1,4-bis(γ-aminopropyldimethyldecyl)benzene , bis(4-aminobutyl)tetramethyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, diamine hydrazine represented by the following formula (5) Oxyalkane compounds, etc. These may be used alone or in combination of two or more. From the standpoint of lowering the warpage after baking, the diamines are preferably formulated in an amount of from 0 mol% to 50 mol% relative to the total number of moles of the diamine.

[化10]

When the polyimide precursor is synthesized, the polyamine precursor may be blocked with a monofunctional acid anhydride, a monofunctional carboxylic acid or a monofunctional amine as needed.

Further, a part of the carboxyl group of the polyimide precursor of the present invention may be partially esterified by using a well-known compound such as an alcohol compound and a method.

The polyimine precursor of the present invention can be prepared into a photosensitive polyimide intermediate composition by blending (B) a sensitizer and (C) an organic solvent.

(B) sensitizer

The photosensitive polyimine precursor composition of the present invention is formulated as a sensitizer by compounding an acid which generates an acid by irradiation with active light. The sensitizer is not particularly limited as long as it generates an acid by irradiation with active light. Among them, a compound containing a quinonediazide structure such as a benzophenonediazide compound or a naphthoquinonediazide compound is preferred. For example, those described in the specification of U.S. Patent No. 2,797,213 and U.S. Patent No. 3,669,658 can be used. Among them, preferred are ester compounds of a phenol compound with 1,2-naphthoquinone-2-diazide-4-sulfonic acid or 1,2-naphthoquinone-2-diazide-5-sulfonic acid. These may be used alone or in combination of two or more.

The compounding amount of the sensitizer of the present invention is preferably from 5 parts by mass to 35 parts by mass, more preferably from 10 parts by mass to 30 parts by mass, per 100 parts by mass of the polyamidene precursor. The amount of the sensitizer is preferably from 5 parts by mass or more from the viewpoint of exhibiting photosensitivity and inhibiting dissolution in a developing solution containing an alkaline aqueous solution, and is preferably from the viewpoint of sensitivity and toughness of the coating layer. It is 35 parts by mass or less.

(C) organic solvent

Examples of the organic solvent used in the present invention include N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and γ-butyl. Lactone, dimethyl alum. Further, a solvent having a boiling point lower than the solvents may be optionally adjusted. Foaming during drying can be suppressed by blending a low boiling point solvent. Specific examples of the low boiling point solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, and triethyl ethane. Alcohols such as diol, propylene glycol or hexanediol, 1,4-dioxane, trioxane, diethyl acetal, 1,2-dioxolane, diethylene glycol dimethyl ether, tetrahydrofuran, benzene Ethers such as methyl ether and triethylene glycol dimethyl ether, ethyl acetate, methyl benzoate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate Ester, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, diethylene glycol Alcohol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diacetate and other esters, n-heptane, n-octane, cyclohexane, benzene, toluene, xylene, B Hydrocarbons such as benzene and diethylbenzene. The amount of the organic solvent to be added is preferably from 25 parts by mass to 900 parts by mass, more preferably from 100 parts by mass to 400 parts by mass, per 100 parts by mass of the polyamidene precursor. When the amount is more than 900 parts by mass, it is difficult to maintain the film thickness after coating, and if it is less than 25 parts by mass, the polyimide precursor is not completely dissolved.

(D) Dissolution inhibitor

The dissolution inhibitor may be formulated as needed in the photosensitive polyimide intermediate composition of the present invention. The dissolution in the developer containing the alkaline aqueous solution of the polyimide precursor can be inhibited by formulating the dissolution inhibitor. The dissolution inhibitor of the present invention means a compound which is hydrogen-bonded to a carboxyl group or a phenolic hydroxyl group of a polyimide precursor. By hydrogen bonding of a carboxyl group or a phenolic hydroxyl group of the polyimide precursor to the dissolution inhibitor, blocking with the developer, and in combination with the hydrophobicity of the compound, the polyimine precursor can be inhibited. Dissolved.

Examples of the compound having a group bonded to a carboxyl group or a phenolic hydroxyl group include a carboxylic acid compound, a carboxylic acid ester compound, a guanamine compound, and a urea compound. From the viewpoint of the dissolution inhibiting effect and the storage stability in the developing solution containing an aqueous alkaline solution, a compound represented by the following formula (6) is preferred, and a guanamine compound or a urea compound is further preferred.

[11]

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

Examples of the guanamine compound include N,N-diethylacetamide, N,N-diisopropylformamide, N,N-dimethylbutylguanamine, and N,N-dibutyl. Ethylamine, N,N-dipropylacetamide, N,N-dibutylformamide, N,N-diethylpropionamide, N,N-dimethylpropionamide, N,N '-Dimethoxy-N,N'-dimethylglucamine, N-methyl-ε-caprolactam, 4-hydroxyphenylbenzamide, salicylamine, salicylate Aniline, acetophenone, 2'-hydroxyacetanilide, 3'-hydroxyacetanilide, 4'-hydroxyacetanilide.

Among them, it is preferable from the viewpoint that the low-glass transition point of the photosensitive layer and the film obtained by baking the photosensitive layer is controlled, and the solubility in the developing solution containing an alkaline aqueous solution is high and the residual film ratio is high. It is a compound having a phenolic hydroxyl group, more preferably a guanamine compound having a phenolic hydroxyl group. Specific examples thereof include 4-hydroxyphenyl benzoguanamine, 2'-hydroxyethyl anilide, 3'-hydroxyethyl anilide, and 4'-hydroxyethyl anilide. These may be used alone or in combination of two or more.

Examples of the urea compound include 1,3-dimethylurea, tetramethylurea, tetraethylurea, 1,3-diphenylurea, and 3-hydroxyphenylurea. Among them, from the viewpoint of solubility in a developing solution containing an alkaline aqueous solution, high residual film rate, a photosensitive layer, and a low glass transition point of a film obtained by baking the photosensitive layer, it is preferable. It is a urea compound containing a phenolic hydroxyl group. Specifically, 3-hydroxyphenyl urea is mentioned. These may be used alone or in combination of two or more.

In the case of using a guanamine compound, the dissolution inhibitor of the present invention is preferably formulated in an amount of 0.1 mol to 2.0 mol based on the carboxyl group of the polyimine precursor and 1 mol of the phenolic hydroxyl group from the viewpoint of exhibiting a dissolution inhibiting effect. More preferably, it is formulated from 0.15 mol to 1.5 mol.

In the case of using a urea compound, the dissolution inhibitor of the present invention is preferably from 0.1 mol to 2.0 mol, based on the carboxyl group of the polyimine precursor and 1 mol of the phenolic hydroxyl group, from the viewpoint of exhibiting a dissolution inhibiting effect. From the viewpoint of exhibiting a dissolution inhibiting effect and exhibiting the toughness of the resin obtained by baking, it is more preferable to formulate 0.15 mol to 1.5 mol.

Further, in the case of using both the guanamine compound and the urea compound, the total amount of the guanamine compound and the urea compound is relative to the carboxyl group of the polyimide precursor and the phenolic hydroxyl group of 1 mol from the viewpoint of the dissolution inhibiting effect. Preferably, it is in the range of 0.1 mol to 1.5 mol.

(E) phenolic compound

The photosensitive polyimine precursor composition of the present invention may be formulated with a phenol compound as needed. The phenol compound contains a compound represented by the following general formula (7) and the following from the viewpoint of reducing the warpage of the film including the baked film and the substrate, and controlling the solubility in the alkaline aqueous solution. A phenolic compound of the structure of the formula (8) (as a component which is not equivalent to the dissolution inhibitor of the present application).

[化12]

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

[Chemistry 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)

Specific examples thereof include dihydroxydiphenylmethane, 4,4'-oxydiphenol, 1,4-bis(3-hydroxyphenoxy)benzene, and 1,3-bis(4-hydroxyphenoxy). a nucleus such as benzene, 1,5-bis(o-hydroxyphenoxy)-3-oxapentane or α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene , tris(hydroxyphenyl)methane, tris(hydroxyphenyl)ethane, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-α,α-dimethylbenzyl} A trinuclear body such as phenol, a polynuclear body represented by the following structural formula (a) to structural formula (h). These phenol compounds may be used singly or in combination of two or more.

[Chemistry 14]

The compounding amount of the phenol compound of the present invention is preferably from 1 part by mass to 30 parts by mass, more preferably from 5 parts by mass to 20 parts by mass, per 100 parts by mass of the polyamidene precursor. When the amount is less than 1 part by mass, it is difficult to suppress the solubility in the developing solution containing the alkaline aqueous solution, and if it is more than 30 parts by mass, the photosensitive layer of the photosensitive dry film obtained after the solvent removal step becomes brittle.

(F) plasticizer

In the photosensitive polyimide intermediate composition of the present invention, a compound represented by the following formula (9) can be suitably used as the plasticizer.

[化15]

(R ₁₂ to R ₁₄ include an organic group of an ethylene glycol chain and/or a propylene glycol chain, which may be the same or different)

Specific examples thereof include compounds represented by the following structural formulae (i) and (j), but are not limited thereto. Further, these compounds may be used singly or in combination of two or more kinds.

[Chemistry 16]

(d is an integer of 0 or more, and e is an integer of 0 or more)

The compounding amount of the plasticizer of the present invention is preferably from 1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 10 parts by mass, per 100 parts by mass of the polyamidene precursor. When the amount is 1 part by mass or more, the effect of reducing warpage is exhibited, and when it is 30 parts by mass or less, the desired pattern is obtained without adversely affecting developability.

(G) crosslinker

In the present invention, a crosslinking agent can be blended for the purpose of improving the toughness of the film after baking. The crosslinking agent is preferably a tetracarboxylic acid compound or a tetracarboxylic acid ester compound represented by the following formula (10), or a polyfluorene imine precursor represented by the following formula (11) or a polyethylenimine precursor ester compound of a carboxyl group.

[化17]

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

[化18]

(R ₂₀ , R ₂₂ and R ₂₄ are tetravalent organic groups, which may be the same or different. R ₂₁ and R ₂₃ are divalent organic groups, which may be the same or different. R ₂₅ to R ₃₂ are hydrogen or carbon number. The monovalent organic group of 1 to 20 may be the same or different. g is an integer of 0 to 100)

From the viewpoint of exhibiting a crosslinking effect, the blending amount of the crosslinking agent of the present invention is preferably from 0.1 mol to 1.5 mol, more preferably 0.5, relative to the molar number of the residual amine group of the polyimide precursor. Mol to 1.1 mol. The amount of residual amine groups can be calculated using high performance liquid chromatography.

(H) hot base generator

The photosensitive polyamidene precursor composition of the present invention may contain a thermal base generator as needed. The hot base generator refers to a compound which generates a base by heating. For example, it is obtained by making a salt structure with an amine group such as an amine compound such as an amine and an acid such as a sulfonic acid, protecting it with a dicarbonate compound, and protecting it with a chlorochemical compound. Thereby, it is stable without being alkaline at room temperature, and can be deprotected by heating to prepare a caustic soda generating agent which generates alkali. Further, the baking temperature of the polyimide precursor can be set to a relatively low temperature by blending the hot base generator.

Specific examples of the hot base generator include U-CAT (registered trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851 (above, trade name, manufactured by San-Apro Co., Ltd.), N- (isopropoxycarbonyl)-2,6-dimethylpiperidine, N-(t-butoxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2, A compound in which 6-dimethyl piperidine or an amine group of an aromatic diamine is protected by dibutyl dicarbonate or the like. Among these, N-(isopropoxy group) is preferred from the viewpoints of storage stability of the photosensitive polyimide intermediate composition, molecular weight stability of solvent removal, alkali solubility, and ion mobility. Carbonyl)-2,6-dimethylpiperidine, N-(t-butoxycarbonyl)-2,6-dimethylpiperidine, N-(benzyloxycarbonyl)-2,6-dimethyl a compound in which an amine group of piperidine or 4,4-diaminodiphenyl ether is protected by dibutyl dicarbonate, a compound of 3,4'-diaminodiphenyl ether is protected by dibutyl dicarbonate, A compound protected by dibutyl dicarbonate of an amine group of 1,3-bis(3-aminophenoxy)benzene, an amine group of 1,3-bis(4-aminophenoxy)benzene by dicarbonate Butyl ester-protected compound, compound of bis(4-aminobenzoic acid) 1,3-propanediester, protected by dibutyl dicarbonate, 1,4-bis(4-aminophenoxy)pentane A compound in which the amine group of the alkane is protected by dibutyl dicarbonate. This compound can be synthesized, for example, by a method well known in Chmistry Letters Vol. 34, No. 10 (2005).

The amount of the hot base generator of the present invention is preferably from 0.5 part by mass to 30 parts by mass, more preferably from 100 parts by mass to 30 parts by mass, per 100 parts by mass of the polyimine precursor, from the viewpoint of the promotion of the imidization and the development performance. It is 0.5 parts by mass to 20 parts by mass.

(I) Phosphate compound

The phosphate compound can be formulated as needed in the photosensitive polyimide intermediate composition of the present invention. These compounds function as a flame retardant, a dissolution aid or a plasticizer for the photosensitive polyimide intermediate composition.

As the phosphate 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.

[Chemistry 19]

(R ₃₃ to R ₃₅ represent an organic group having a carbon number of 1 or more, and may be the same or different)

[Chemistry 20]

(R ₃₆ to R ₃₉ represent an organic group having a carbon number of 1 or more, and may be the same or different)

[Chem. 21]

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

In view of improving the flame retardancy or plasticity of the photosensitive polyimide intermediate composition, R ₃₃ to R ₃₅ in the above formula (12) or R ₃₆ to R ₃₉ in the above formula (13) Preferred are organic groups selected from the group consisting of methyl, ethyl, butyl, 2-ethylhexyl, butoxyethyl, phenyl, tolyl, xylyl, and aminophenyl.

Further, in consideration of the thermal stability and the warpage improving effect of the photosensitive dry film, R ₄₀ in the above formula (14) is preferably selected from the group consisting of hydrogen, dihydroxyphenyl, and dibutylhydroxybenzyl. An organic group in an organic group containing a (meth) acrylate group. Further, in consideration of the compatibility with the resin varnish or the warpage improving effect at the time of photosensitive dry film formation, R _{40 is} preferably hydrogen.

These phosphate compounds may be formulated individually or in combination of two or more. The amount of the phosphate compound is preferably from 1 part by mass to 30 parts by mass, more preferably from 1 part by mass to 20 parts by mass. When the amount is 1 part by mass or more, the plasticity is exhibited. When the amount is 30 parts by mass or less, the portion of the photosensitive polyimide intermediate composition that is not irradiated with the active light is difficult to be used in the developer containing the alkaline aqueous solution. It is eroded and a good radiographic image can be obtained.

(J) organophosphorus compounds

The photosensitive polyimine precursor composition of the present invention can be formulated with an organophosphorus compound represented by the following formula (15). The resin pattern obtained by baking can be imparted with flame retardancy by blending the organophosphorus compound.

[化22]

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

The amount of the organophosphorus compound is preferably from 1 part by mass to 30 parts by mass, and more preferably from 3 parts by mass to 25 parts by mass. When the amount is 1 part by mass or more, the flame retardancy is exhibited, and when it is 30 parts by mass or less, the resin pattern obtained after baking becomes tough.

(K) Other ingredients

The photosensitive polyimine precursor composition of the present invention may optionally contain an imidazole compound, a triazole compound, a tetrazole compound or a thioether compound. The adhesion to the copper substrate can be improved by blending the compounds.

The compounding amount of the compound is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass. When the amount is 0.1 part by mass or more, the adhesiveness is improved. When the amount is 10 parts by mass or less, a good radiation image can be obtained without adversely affecting developability.

In the photosensitive polyimine precursor composition of the present invention, for the purpose of improving the wettability with the support film, an alcohol such as ethanol, 2-propanol or ethylene glycol, ethyl lactate or benzene may be blended as needed. An ester such as methyl formate or ethylene glycol monopropyl ether acetate; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; an ether such as n-butyl ether, tetrahydrofuran or dioxane; A glycol ether such as diethyl ether or propylene glycol monoethyl ether.

The photosensitive polyimide intermediate precursor composition of the present invention can be used as a cover layer. The cover layer refers to a protective film that protects wiring formed on a silicon wafer, a copper foil laminate, an FPC or the like.

(Adjustment of photosensitive polyimide intermediate composition)

The photosensitive polyimine precursor composition of the present invention utilizes a spin mixer, a non-foaming kneader, and a tri-motor having a stirring blade by mixing the above-mentioned polyimide precursor and various compounds in a suitable container. It is obtained by stirring until it is completely dissolved.

(Manufacture of resin pattern)

In the present invention, a photosensitive dry film can be produced using a photosensitive polyimide intermediate composition to form a resin pattern. This resin pattern can be formed by the following steps.

(1) a step of applying a photosensitive polyimide intermediate composition onto a film substrate, followed by solvent removal to prepare a photosensitive dry film

The photosensitive dry film is obtained by applying a photosensitive polyimide intermediate composition to a support film (film substrate), drying the solvent, and forming a photosensitive layer. As the support film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene/cyclodecene copolymer, or the like can be used. The support film may be subjected to surface treatment for controlling the wettability of the photosensitive polyimide precursor composition or the peeling property of the photosensitive layer obtained from the photosensitive polyimide precursor composition. . Examples of the surface treatment method include corona treatment, frame treatment, plasma treatment, and surface modification using polyfluorene oxide, an alkyd resin, or an olefin resin. Further, in consideration of coatability, adhesion, rollability, toughness, cost, and the like, the thickness of the carrier film is usually 15 μm to 100 μm, preferably 15 μm to 75 μm.

The coating of the photosensitive polyimide precursor composition may be carried out on the above support film using a reverse roll coater or a gravure roll coater, a comma coater, a lip coater, A slit extrusion coater or the like is known as a method.

The solvent removal can be carried out by drying the solvent (using a hot air drying or a far infrared ray, a near infrared ray dryer). The drying temperature is preferably from 50 ° C to 120 ° C from the viewpoint of suppressing the molecular weight of the dye, and is preferably from 50 ° C to 110 ° C from the viewpoint of stability of the sensitizer. The film thickness of the photosensitive layer obtained by the solvent removal is preferably from 5 μm to 100 μm, more preferably from 5 μm to 50 μm. From the viewpoint of insulation reliability, the film thickness is preferably 5 μm or more, and from the viewpoint of obtaining a good radiation image, the film thickness is preferably 100 μm or less. Here, if the ratio (Mw2/Mw1) between the weight average molecular weight (Mw1) of the polyamidene precursor varnish and the weight average molecular weight (Mw2) after desolvation of 120 ° C or less is 0.7 or more, the following effects are achieved. : Even if the photosensitive dry film is bent after solvent removal, there is no breakage of the photosensitive layer.

Further, a cover film can be laminated on the photosensitive dry film to form a photosensitive laminated film. The adhesion of the photosensitive layer to the support film can be prevented by laminating the film. As the cover film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene/cyclodecene copolymer can be used.

(2) a step of pressing a photosensitive dry film onto a substrate provided with a pattern to form a photosensitive layer

The photosensitive dry film is superposed on a circuit-formed surface (a substrate on which a pattern is placed) such as FPC, and is heated from 40 ° C to 130 ° C by a well-known method such as planar lamination, roll lamination, or vacuum pressing. Preferably, it is heated from 60 ° C to 120 ° C and laminated (pressure-bonded) with a pressure of 0.2 MPa to 5 MPa, whereby the photosensitive layer can be laminated.

In this case, when the photosensitive dry film is a photosensitive laminated film of a laminated cover film, the cover film is peeled off before lamination. When the laminable temperature is 40° C. or higher, the alignment is not complicated by adhesion when the position is aligned before lamination, and the sensitizing agent is not decomposed by setting the laminable temperature to 130° C. or less. Can be laminated. Furthermore, the laminable temperature means that there is no problem such as residual bubbles, and it can be sufficiently embedded in the pattern, and the photosensitive layer can be controlled so that the photosensitive polyimide precursor composition does not flow excessively and flows out of the pattern. Viscosity.

Further, by making the glass transition point (hereinafter referred to as Tg) of the photosensitive layer lower than the lamination temperature, lamination of the photosensitive dry film can be suitably performed. After lamination of the photosensitive layer, the support film may or may not be peeled off. In the case where the support film is not peeled off after lamination, it is peeled off after the exposure step.

(3) Step of irradiating the photosensitive layer with active light

In order to form a micropore or a fine width line, the photosensitive layer is exposed by a photomask having an arbitrary pattern. The amount of exposure varies depending on the composition of the photosensitive polyimide intermediate composition, and is usually from 100 mJ/cm ² to 3,000 mJ/cm ² . Examples of the active light rays used at this time include X-rays, electron beams, ultraviolet rays, visible rays, and the like. As the light source of the active light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, or the like can be used. In the present invention, it is preferred to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp. The method of irradiating the active light may be any one of adhesion exposure and projection exposure.

(4) Step of developing with an alkaline aqueous solution

After the exposure, development is carried out by a known method such as a dipping method or a spraying method using a developing solution to obtain a radiographic image. As the developer, an aqueous alkaline solution such as a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, or a tetramethylammonium hydroxide aqueous solution can be used. Further, in this step, it is preferred to perform development while facing the developer. By managing the development temperature, the development time can be controlled so that the shape of the obtained radiation image can be maintained. From these viewpoints, the temperature of the developer is preferably from 20 ° C to 60 ° C, and more preferably from 25 ° C to 50 ° C.

(5) a step of rinsing with at least one solvent selected from the group consisting of water and an acidic aqueous solution

After the development, the cleaning is carried out by a well-known method such as a dipping method or a spraying method. As the rinsing liquid, water or an organic solvent added to water can be used. In this step, it is preferred to maintain the rinsing liquid at an appropriate temperature. Thereby, the residue on the substrate or the resin can be removed after development. The temperature of the rinsing liquid is preferably from 15 ° C to 60 ° C, and more preferably from 20 ° C to 50 ° C from the viewpoint of removing the residue. After washing with a rinse liquid, it can be washed with an aqueous solution of an inorganic acid or an aqueous solution of an organic acid. Specific examples of the inorganic acid aqueous solution include a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a phosphoric acid aqueous solution, and a boric acid aqueous solution. Specific examples of the organic acid aqueous solution include a formic acid aqueous solution, an acetic acid aqueous solution, a citric acid aqueous solution, and an aqueous lactic acid solution. The cleaning time by the inorganic acid aqueous solution or the organic acid aqueous solution is preferably from 5 seconds to 120 seconds, and more preferably from 10 seconds to 60 seconds, from the viewpoint of cleaning efficiency. In the case of rinsing with an acidic aqueous solution, it is preferred to rinse the acidic aqueous solution with water thereafter.

(6) Step of irradiating the entire photosensitive layer with active light

After the rinsing step, the entire surface of the obtained radiation image can be irradiated with active light. The sensitizer can be decomposed by this step to shorten the time of the subsequent curing step. Further, the light transmittance of the resin pattern obtained after the curing step can be increased. Further, with this step, the residual stress applied between the counter substrate and the photosensitive layer derived from the photosensitive agent can be reduced, and the warpage of the FPC or the multilayer printed wiring board obtained in the resin pattern manufacturing step can be reduced, and the folding endurance can be improved. The exposure amount to be irradiated in this step differs depending on the kind of the photosensitive agent to be used or the film thickness of the photosensitive layer, and is usually from 100 mJ/cm ² to 3,000 mJ/cm ² . For example, when a phthalocyanine diazide compound is used and the film thickness of the photosensitive layer is 25 μm, it is preferably 500 mJ/cm ² or more from the viewpoint of photolysis of the sensitizer. Examples of the active light rays used at this time include X-rays, electron beams, ultraviolet rays, visible rays, and the like. As the light source of the active light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, or the like can be used. Among these, it is preferred to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp. Further, the active light can be irradiated while being heated as needed. From the viewpoint of workability, the heating temperature is preferably from 30 ° C to 130 ° C, and more preferably from 40 ° C to 100 ° C.

(7) Steps of baking at 100 to 400 ° C

The radiation image obtained in the above step is baked, thereby forming a resin pattern. The baking is carried out continuously or in stages at a temperature of from 100 ° C to 400 ° C for from 5 minutes to 5 hours. Then, it can be made into a processed product. In the case of FPC, it is preferred to cure at a temperature ranging from 100 ° C to 200 ° C from the viewpoint of preventing oxidation of wiring. Examples of the processed product obtained in this manner include an FPC, a multilayer printed wiring board, and the like.

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but is not limited by the examples.

(Synthesis of Polyimine Precursor) Synthesis Example 1 Synthesis of Polyimine Precursor (i)

To a three-neck separable flask, 6.4 g of 1,3-bis(3-aminophenoxy)benzene and 62 g of γ-butyrolactone were added and stirred until a homogeneous solution was obtained. Then, 10 g of pentanediol-trimellitic anhydride was added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (i) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (i) solution, and the weight average molecular weight of the obtained polyimine precursor (i) are shown in Table 1.

Synthesis Example 2 Synthesis of Polyimine Precursor (ii)

4.8 g of 1,3-bis(3-aminophenoxy)benzene, 6.8 g of polyoxytetramethylene-di-p-aminobenzoate, 82 g of γ were added to a three-neck separable flask. - Butyrolactone, stirring until it becomes a homogeneous solution. Then, 10 g of pentanediol-trimellitic anhydride was added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (ii) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (ii) solution, and the weight average molecular weight of the obtained polyimine precursor (ii) are shown in Table 1.

Synthesis Example 3 Synthesis of Polyimine Precursor (iii)

9.7 g of 1,3-bis(3-aminophenoxy)benzene, 13.7 g of polyoxytetramethylene-di-p-amino benzoate, 168.8 g were added to a three-neck separable flask. Gamma-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester and 11.5 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (iii) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (iii) solution, and the weight average molecular weight of the obtained polyimine precursor (iii) are shown in Table 1.

Synthesis Example 4 Synthesis of Polyimine Precursor (iv)

8.8 g of 1,3-bis(3-aminophenoxy)benzene, 12.4 g of polyoxytetramethylene-di-p-aminobenzoate, 99.7 g were added to a three-neck separable flask. Gamma-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester and 11.5 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (iv) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (iv) solution, and the weight average molecular weight of the obtained polyimine precursor (iv) are shown in Table 1.

Synthesis Example 5 Synthesis of Polyimine Precursor (v)

To a three-neck separable flask was added 10.0 g of bis(4-aminobenzoic acid) 1,3-propane diester, 13.1 g of polyoxytetramethylene-di-p-amino benzoate, 104.1 g. The γ-butyrolactone is stirred until it becomes a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester and 11.5 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (v) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (v) solution, and the weight average molecular weight of the obtained polyimine precursor (v) are shown in Table 1.

Synthesis Example 6 Synthesis of Polyimine Precursor (vi)

9.8 g of bis(4-aminobenzoic acid) 1,3-propane diester, 12.9 g of polyoxytetramethylene-di-p-amino benzoate, 103.1 g were added to a three-neck separable flask. The γ-butyrolactone is stirred until it becomes a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester and 11.5 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimide precursor (vi) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (vi) solution, and the weight average molecular weight of the obtained polyimine precursor (vi) are shown in Table 1.

Synthesis Example 7 Synthesis of Polyimine Precursor (vii)

9.5 g of bis(4-aminobenzoic acid) 1,3-propane diester, 12.4 g of polyoxytetramethylene-di-p-amino benzoate, 101.0 g were added to a three-neck separable flask. The γ-butyrolactone is stirred until it becomes a homogeneous solution. Then, 10 g of pentanediol-trimellitic anhydride ester and 11.5 g of decanediol-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (vii) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (vii) solution, and the weight average molecular weight of the obtained polyimine precursor (vii) are shown in Table 1.

Synthesis Example 8 Synthesis of Polyimine Precursor (viii)

9.1 g of bis(4-aminobenzoic acid) 1,3-propane diester, 15.4 g of polyoxytetramethylene-di-p-amino benzoate, 107.3 g were added to a three-neck separable flask. The γ-butyrolactone is stirred until it becomes a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester and 11.5 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (viii) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (viii) solution, and the weight average molecular weight of the obtained polyimine precursor (viii) are shown in Table 1.

Synthesis Example 9 Synthesis of Polyimine Precursor (ix)

9.8 g of bis(3-aminobenzoic acid) 1,3-propane diester, 12.9 g of polyoxytetramethylene-di-p-amino benzoate, 103.1 g were added to a three-neck separable flask. Gamma-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester and 11.5 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimide precursor (ix) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (ix) solution, and the weight average molecular weight of the obtained polyimine precursor (ix) are shown in Table 1.

Synthesis Example 10 Synthesis of Polyimine Precursor (x)

To a three-neck separable flask was added 9.8 g of bis(4-aminobenzoic acid) 1,3-propane diester and 12.9 g of poly(1,4-butanediol/3-methyl-1,4- Butylene glycol) ether bis(4-aminobenzoate), 103.1 g of γ-butyrolactone, and stirred until a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester and 11.5 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (x) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (x) solution, and the weight average molecular weight of the obtained polyimine precursor (x) are shown in Table 1.

Synthesis Example 11 Synthesis of Polyimine Precursor (xi)

10.1 g of bis(4-aminobenzoate) 1,3-propane diester and 13.3 g of polyoxytetramethylene-di-p-amino benzoate were added to a three-neck separable flask. 105.7 g of γ-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of butanediol-p-trimellitic anhydride ester and 11.9 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (xi) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xi) solution, and the weight average molecular weight of the obtained polyamidene precursor (xi) are shown in Table 1.

Synthesis Example 12 Synthesis of Polyimine Precursor (xii)

To a three-neck separable flask was added 9.8 g of bis(4-aminobenzoic acid) 1,3-propane diester, 12.9 g of polyoxytetramethylene-di-p-amino benzoate, 110.4 g. The γ-butyrolactone is stirred until it becomes a homogeneous solution. Then, 10 g of pentanediol-trimellitic anhydride ester and 14.6 g of eicosanediol-bis-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, followed by stirring at room temperature for 6 hours. . Then, the polyimine precursor (xii) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyamidene precursor (xii) solution, and the weight average molecular weight of the obtained polyimine precursor (xii) are shown in Table 1.

Synthesis Example 13 Synthesis of Polyimine Precursor (xiii)

9.8 g of bis(4-aminobenzoic acid) 1,3-propane diester, 12.9 g of polyoxytetramethylene-di-p-amino benzoate, 123.9 g were added to a three-neck separable flask. The γ-butyrolactone is stirred until it becomes a homogeneous solution. Then, 10 g of pentanediol-p-trimellitic anhydride ester and 20.4 g of polypropylene glycol-p-trimellitic anhydride were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (xiii) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xiii) solution, and the weight average molecular weight of the obtained polyimine precursor (xiii) are shown in Table 1.

Synthesis Example 14 Synthesis of Polyimine Precursor (xiv)

9.4 g of 1,3-bis(3-aminophenoxy)benzene and 73 g of γ-butyrolactone were added to a three-neck separable flask, and the mixture was stirred until it became a homogeneous solution. Then, 10 g of 4,4'-oxydiphthalic dianhydride was added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimide precursor (xiv) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xiv) solution, and the weight average molecular weight of the obtained polyimine precursor (xiv) are shown in Table 1.

Synthesis Example 15 Synthesis of Polyimine Precursor (xv)

To a three-neck separable flask, 7.1 g of 1,3-bis(3-aminophenoxy)benzene and 64.3 g of γ-butyrolactone were added and stirred until a homogeneous solution was obtained. Then, 10 g of ethylene glycol-bis-p-benzoic acid ester was added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (xv) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xv) solution, and the weight average molecular weight of the obtained polyimine precursor (xv) are shown in Table 1.

Synthesis Example 16 Synthesis of Polyimine Precursor (xvi)

2.7 g of 1,3-bis(3-aminophenoxy)benzene, 26.3 g of polyoxytetramethylene-di-p-aminobenzoate, 91.0 g were added to a three-neck separable flask. Gamma-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of 4,4'-oxydiphthalic dianhydride was added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (xvi) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xvi) solution, and the weight average molecular weight of the obtained polyimine precursor (xvi) are shown in Table 1.

Synthesis Example 17 Synthesis of Polyimine Precursor (xvii)

To a three-neck separable flask was added 2.0 g of 1,3-bis(3-aminophenoxy)benzene, 19.9 g of polyoxytetramethylene-di-p-aminobenzoate, 74.4 g of Gamma-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of ethylene glycol-bis-p-benzoic acid ester was added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (xvii) was obtained by subjecting the product to pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xvii) solution, and the weight average molecular weight of the obtained polyimine precursor (xvii) are shown in Table 1.

(Adjustment of photosensitive polyimide intermediate composition)

First, a specific amount of the polyimide precursor is divided into small portions and placed in a container such as a glass bottle. Then, a specific amount of an additive such as a photosensitizer or a dissolution inhibitor is formulated, and the mixture is stirred by a rotary mixer or the like until uniform. A photosensitive polyimide intermediate precursor composition can be obtained by these operations.

(Measurement of weight average molecular weight) 1: Determination of molecular weight of polyimine precursor

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

2: Determination of weight average molecular weight of photosensitive polyimide intermediate composition

Coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed using a dryer (SPH-201, manufactured by Espec) at 95 ° C for 30 minutes.

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

The molecular weight ratio is calculated by setting the weight average molecular weight of the photosensitive polyimide precursor composition varnish to M1, and setting the weight average molecular weight of the photosensitive polyimide precursor composition after the solvent removal to M2. The molecular weight ratio was calculated by the following formula 1.

Molecular weight ratio = M2/M1

(bending test)

Coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 100 μm (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed by a dryer (SPH-201, manufactured by ESPEC) at 95 ° C for 30 minutes.

Bending test: The film obtained by removing the solvent was bent by 180 degrees (folding), and the cracking and peeling of the photosensitive layer were visually observed. The case where there was no cracking or peeling was recorded as ○, and the case where cracking and peeling occurred was denoted as ×.

(warping evaluation)

Coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed by a dryer (SPH-201, manufactured by ESPEC) at 95 ° C for 30 minutes.

Vacuum pressing: The substrate was obtained by using a polyimide film (Kapton EN-100, trade name, manufactured by Toray-Dupont Co., Ltd.), and using a vacuum press (SA-501, manufactured by Tester Industries, Inc.) to obtain the photosensitivity in the solvent removal step. The dry film was subjected to vacuum pressing at a pressing temperature of 100 ° C, a pressing pressure of 0.5 MPa, a vacuum of 15 kPa, and a pressing time of 1 minute.

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

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

(Example 1)

Evaluation of Photosensitive Polyimine Precursor Compositions Containing Polyimine Precursors and Sensitizers

10 g of the polyimine precursor solution obtained in Synthesis Examples 1 to 3, and 20 parts by mass of the quinonediazide compound (Formula 16) as a sensitizer with respect to the polyimide intermediate precursor, The mixture was mixed in a ratio shown in Table 2, placed in a 20 cc glass bottle, and stirred by a rotary mixer (MR-5, manufactured by As One Co., Ltd.) until uniform, to obtain a photosensitive polyimide intermediate composition (1). To 3). The evaluation results are shown in Table 2.

[化23]

(Example 2)

Evaluation of Photosensitive Polyimine Precursor Composition Using 3'-Hydroxyacetanilide for Dissolution Inhibitor

10 g of the polyimine precursor solution obtained in Synthesis Examples 1 to 3, and 20 parts by mass of the quinonediazide compound (Formula 16) 0.42 g as a sensitizer with respect to the polyimine precursor. 0.25 g of 12.5 parts by mass of 3'-hydroxyacetanilide relative to the polyimide precursor, mixed at a ratio shown in Table 3, placed in a 20 cc glass bottle, and rotated using a rotary mixer (MR-5) , manufactured by As One), stirred until uniform, to obtain a photosensitive polyimide intermediate composition (4 to 6). The evaluation results are shown in Table 3.

[化23]

(Example 3)

Evaluation of Photosensitive Polyimine Precursor Composition Using Phenol Compounds

10 g of the polyimine precursor solution obtained in Synthesis Examples 1 to 3, and 20 parts by mass of the sensitizer relative to the polyamidene precursor, represented by the above formula (16) 0.42 g of the azide compound and 0.22 g of the phenol compound represented by the following general formula (17) in an amount of 20 parts by mass based on the polyimine precursor, and mixed in the ratio shown in Table 4, and placed in a ratio of 20 cc. In the glass bottle, the mixture was stirred until uniform by a rotary mixer (MR-5, manufactured by As One Co., Ltd.) to obtain a photosensitive polyimide intermediate composition (7 to 9). The evaluation results are shown in Table 4.

[Chem. 24]

(Comparative Example 1)

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

(Comparative Example 2)

The photosensitive polyimide intermediate precursor compositions (12 to 13) shown in Table 2 were obtained in the same manner as in Example 2 except that 10 g of the polyimine precursor solution obtained in Synthesis Examples 14 to 15 were used. . The evaluation results are shown in Table 3.

(Comparative Example 3)

The photosensitive polyimide intermediate 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 polyimine precursor solution obtained in Synthesis Examples 14 to 15 were used. . The evaluation results are shown in Table 4.

In the case where the photosensitive polyimide intermediate composition is used for a cover film or the like of a flexible printed circuit board, it is necessary to perform lithography using a developing solution containing an alkaline aqueous solution to obtain a desired pattern. Further, in addition to the fact that the molecular weight of the composition does not change with time, the adhesiveness is also excellent, and the laminate having the cover film after baking has no warpage, and even if it is bent, no peeling or cracking occurs, and the laminated body does not burn. .

(Performance Evaluation of Photosensitive Polyimine Precursor Composition) 1) Evaluation of material stability

Coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed by a dryer (SPH-201, manufactured by ESPEC) at 95 ° C for 30 minutes.

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

The molecular weight ratio is calculated by setting the weight average molecular weight of the photosensitive polyimide precursor composition varnish to M1, and setting the weight average molecular weight of the photosensitive polyimide precursor composition to M2 after solvent removal. The molecular weight ratio was calculated by the following formula 1.

Molecular weight ratio = M2/M1

2: lithography performance evaluation

Coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed by a dryer (SPH-201, manufactured by ESPEC) at 95 ° C for 30 minutes.

Vacuum pressing: The FCCL was first washed with a 15% by weight aqueous solution of sodium persulfate. Then, using a vacuum press (SA-501, manufactured by Tester Industries, Inc.), the photosensitive dry film obtained in the solvent removal step was pressed at a temperature of 100 ° C, a pressing pressure of 0.5 MPa, a vacuum of 15 kPa, and a pressing time of Vacuum pressing was carried out for 1 minute.

Active light irradiation: The support film of the laminate obtained in the vacuum pressing step was peeled off, and ultraviolet rays were irradiated under the conditions of an exposure amount of 1.5 J/cm ² using an ultrahigh pressure mercury lamp (HMW-201 KB, manufactured by Oak Co., Ltd.).

Photomicrograph: Using a spray type developing machine, the developing solution was measured using a 1 wt% aqueous solution of sodium carbonate at a developing temperature of 30 ° C and a spray pressure of 0.18 MPa, and the time until the UV irradiated portion was completely dissolved (hereinafter referred to as a breakpoint) (break point)). Then, development was carried out at a development time of 1.2 times the break point. After the development, the cleaning time was x 1/3 in distilled water using a spray washer, and further washed with a 0.2 wt% aqueous sulfuric acid solution for 30 seconds.

Micro-film performance: The lithography performance was judged based on development time, residual film rate, and pattern shape.

Development time: A photosensitive polyimide intermediate composition having a development time of 90 seconds or less is referred to as "○", and a photosensitive polyimide intermediate composition of more than 90 seconds is referred to as "X".

Residual film rate measurement: The film thickness of the photosensitive layer before development was set to T1, and the film thickness of the photosensitive layer after development was set to T2, and it computed by the following mathematical formula.

Residual film rate = T2 / T1 × 100 (%)

Pattern shape: An optical microscope (ECLIPS LV100, manufactured by Nikon Corporation) was used, and the pattern after lithography was observed in a shape of a 100 μm circular pattern with a clear field of view and 100 times. The person who holds the pattern shape is denoted by ○, and the person who deforms the pattern is denoted by ×.

3: Viscosity evaluation of photosensitive dry film

Coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed by a dryer (SPH-201, manufactured by ESPEC) at 95 ° C for 30 minutes.

Viscosity evaluation: The adhesion of the photosensitive layer after solvent removal was evaluated by palpation. The person who has fingerprinted is marked as ×, and the person who has not fingerprinted is marked as ○.

4: Evaluation of folding resistance

Curing: After lithography, curing was carried out under the conditions shown in Table 5 using a dryer (SPH-201, manufactured by ESPEC).

Bending test: The film obtained after curing was bent (folded and folded) by 180 degrees to visually observe cracking and peeling of the cover film. The case where there was no cracking or peeling was recorded as ○, and the case where cracking and peeling occurred was denoted as ×.

5: Warpage evaluation

Coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed by a dryer (SPH-201, manufactured by ESPEC) at 95 ° C for 30 minutes.

Vacuum pressing: The substrate was obtained by using a polyimide film (Kapton EN-100, trade name, manufactured by Toray-Dupont Co., Ltd.), and using a vacuum press (SA-501, manufactured by Tester Industries, Inc.) to obtain the photosensitivity in the solvent removal step. The dry film was subjected to vacuum pressing at a pressing temperature of 100 ° C, a pressing pressure of 0.5 MPa, a vacuum of 15 kPa, and a pressing time of 1 minute.

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

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

6: Flame retardancy evaluation

It was carried out in the same manner as the evaluation of warpage until application and solvent removal.

Vacuum pressing: The substrate was obtained by using a polyimide film (Kapton EN-100, trade name, manufactured by Toray-Dupont Co., Ltd.), and using a vacuum press (SA-501, manufactured by Tester Industries, Inc.) to obtain the photosensitivity in the solvent removal step. The dry film was subjected to vacuum pressing on both sides of the polyimide film at a pressing temperature of 100 ° C, a pressing pressure of 0.5 MPa, a vacuum of 15 kPa, and a pressing time of 1 minute.

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

Flame retardancy test: The film obtained in the baking step was cut to a width of 1 cm and a length of 5 cm. Then, one of the test pieces was visually observed to be on fire and the fire spread. The sample which was extinguished in the middle was recorded as ○, and the sample which was completely burned was recorded as ×.

(Examples 4 to 22)

With respect to 10 g of the polyimine precursor solution obtained in Synthesis Examples 2 to 13, various additives were mixed at a ratio shown in Table 6-1, placed in a 20 cc glass bottle, and a rotary mixer (MR-5) was used. , manufactured by As One), stirred until uniform, to obtain a photosensitive polyimide intermediate composition (16 to 34). The evaluation results of the photosensitive polyimide intermediate composition are shown in Table 7-1.

(Comparative Examples 4 to 7)

With respect to 10 g of the polyimide intermediate precursor solution obtained in Synthesis Examples 16 to 17, various additives were mixed in a ratio shown in Table 6-2, placed in a 20 cc glass bottle, and a rotary mixer (MR-5) was used. , manufactured by As One), stirred until uniform, to obtain a photosensitive polyimide intermediate composition (35 to 38). The evaluation results of the photosensitive polyimide precursor compositions are shown in Table 7-2.

As shown in Tables 2 to 4, Examples 1 to 3 using the polyimine precursor of the present invention showed no decrease in molecular weight (M2/M1). Moreover, the curling strength is also good. The reason for this is considered to be that the decomposition of the polyimine precursor in the case of solvent removal is suppressed by using the acid dianhydride of the present invention, and the molecular weight is suppressed from being lowered. On the other hand, Comparative Examples 1 to 3, which are known to use other acid dianhydrides, have not only a decrease in molecular weight but also a decrease in the curling strength.

Further, as shown in Table 7-1 and Table 7-2, Examples 4 to 22 using the polyimide intermediate composition of the present invention showed a good residual film ratio. In particular, in Example 8, the dissolution inhibitor was not added and the residual film ratio was 90%. The reason for these results is generally considered to be that the decomposition of the polyimide precursor in the development step is suppressed by using the acid dianhydride of the present invention. Examples 4 to 22 showed good adhesion. On the other hand, under any of the conditions of using other acid dianhydrides, the residual film ratio was lowered and the viscosity was poor.

[Industrial availability]

The polyimine precursor of the present invention can be suitably used as a surface protective film for a semiconductor device, an interlayer insulating film, and an insulating film for rewiring, a protective film of a device having a bump structure, an interlayer insulating film of a multilayer circuit, and flexibility. Top coat of copper foil board, liquid crystal alignment film, etc.

Claims (11)

A polyimine precursor comprising an acid dianhydride represented by the following formula (1) and a diamine represented by the following formula (2): (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); (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 polyimine precursor of claim 1, wherein the polyimine precursor comprises an acid dianhydride represented by the following formula (3): (a represents an integer of 1 to 20; b represents an integer of 3 to 30; and R ₃ represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms). The polyimine precursor of claim 1, wherein the polyimine precursor comprises a diamine represented by the following 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; and c represents an integer of 2 to 30). The polyimine precursor of claim 1, wherein the polyimine precursor comprises an acid dianhydride represented by the following formula (3): (a represents an integer of 1 to 15; b represents an integer of 5 to 20; and R ₃ represents a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms). The polyimine precursor of claim 3, wherein the diamine represented by the above formula (4) is from 25 mol% to 75 mol% in all diamine components. The polyimine precursor of claim 1, wherein the ratio (Mw2/Mw1) between the weight average molecular weight (Mw1) of the varnish and the weight average molecular weight (Mw2) after desolvation at 120 ° C or lower is 0.7 or more. A photosensitive polyimide intermediate composition comprising 100 parts by mass of the polyimine precursor of claim 1 or 4, and 5 parts by mass to 35 parts by mass of a sensitizer. The photosensitive polyimide intermediate precursor composition of claim 7, wherein the sensitizer comprises a quinonediazide structure. The photosensitive polyimide intermediate precursor composition of claim 7, which comprises a dissolution inhibitor having a phenolic hydroxyl group. A photosensitive dry film obtained by applying a photosensitive polyimide intermediate composition according to claim 7 to a support film, performing a solvent removal, and then laminating a cover film. A flexible printed circuit board characterized in that it is formed using the photosensitive dry film of claim 10.