TW201006867A - Polyimide precursor, photosensitive polyimide precursor composition, photosensitive dry film, and flexible printed circuit board using those materials - Google Patents

Abstract

Disclosed is a polyimide precursor: which enables the production of such a photosensitive dry film that has no tackiness, causes no cracking in a photosensitive layer thereof when folded after removal of a solvent therefrom, and can achieve good lithography thereon; which can be applied to a FPC that causes less warpage after baking; and which can exhibit flame retardancy without the need of adding any halogen compound thereto. Also disclosed is a photosensitive polyimide precursor composition. Further disclosed is a photosensitive dry film. Still further disclosed is a flexible printed circuit board produced by using any one of the aforementioned materials. The polyimide precursor is characterized by comprising an acid dianhydride represented by general formula (1) [wherein X represents a bivalent organic group having a C3-30 alkylene group; and R1 represents a hydrogen atom, a C1-10 univalent alkyl group, an alkoxy group or a halogen group].

Description

201006867 VI. Description of the Invention: 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 . [Prior Art] In recent years, it has been called a flexible printed circuit board (hereinafter, also referred to as "FPC (Flexible)

Printed Circuit (Flexible Printed Circuit).") The film-shaped printed substrate tends to be versatile. The substrate is formed in a wire-processed FCCL (Flexible Cupper)

Clad Laminate (flexible copper clad laminate) has a structure composed of a polyimide film or the like, and is mainly used for a mobile phone, a notebook computer, a digital camera, and the like. FPC maintains its function even when it is bent, so 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. .

A 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 fineness 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. 139901.doc 201006867 Among the photosensitive coating materials, 'the photosensitive ruthenium layer using the polyimide intermediate precursor' is expected to be derived from the viewpoint of resistance to f-resistance, heat resistance and electrical insulation of the styrene. Excellent cover. For example, Patent Document 1 discloses a heat-resistant adhesive using four acid two needles and a diamine. Further, JP 2 discloses that a film of a thermoplastic precursor resin is formed by using a film of a polyimide intermediate precursor, and Patent Document 3 discloses a photosensitive top coat material comprising polyamine.专利, Patent Document 4 discloses an adhesive film containing a specific acid term. However, in the case of using the photosensitive coating of the (iv) imine precursor, the problem of the stickiness of the photosensitive dry film may occur, or the solvent may be used due to the solvent removal accompanying the formation of the photosensitive dry film. The decrease in the molecular weight of the body is caused by the problem that the photosensitive dry film obtained is bent when the photosensitive dry film is bent. 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 aqueous test solution, the film thickness of the pattern is reduced, and the pattern shape is deformed. X, in the step of converting the polyimine precursor to polyimine, the stress caused by the ring closure reaction accompanying the desolvation or the sulfhydryl imidization of the polyimide precursor will 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 distortion of the FPC having a cover 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, it is desirable to exhibit flame retardancy by an element. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The present invention has been developed in view of the above aspects, and an object thereof is to provide a case for use in an FPC. A polyimide polyimide precursor, a photosensitive polyimide precursor precursor composition, a photosensitive dry film, and a flexible printed circuit board using the same, which have a small surface curvature and excellent folding property after FPC. [Technical means for solving the problem] 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 a carbon number of 3 to 30. The core represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 10, an alkoxy group, or a halogen group) Among the imine precursors, a diamine represented by the following formula (2) is preferred. 139901.doc 201006867 [Chemical 2]

(Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. R2 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group) Among the imine precursors, it is preferred to contain 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. R3 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]

(4) (Z series is a 2 to 20 alkylene group. R4 represents a hydrogen atom, a carbon number of 1 to 1 〇 139901.doc 201006867 of a monovalent alkyl group, a hospitaloxy group, or a halogen group. c represents 2 In the polyimine precursor of the present invention, it is preferred to include an acid dianhydride represented by the following formula (3). [Chemical 5]

L. Fine Hi

(a represents an integer of 1 to 15. b represents an integer of 5 to 20. & represents a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 10) Among the polyamidene precursors of the present invention, preferably The diamine represented by the above formula (4) is from 25 mol% to 75 mol% in all the diamine components. The photosensitive polyimide intermediate composition of the present invention is characterized in that it contains 1 part by mass of the above polyimine precursor and 5 to 3 parts by mass of a light-sensitive agent. In the photosensitive polyimine precursor composition of the present invention, it is preferred that the sensitizer contains a awake azide structure. In the photosensitive polyimine precursor composition of the present invention, a compound having a desired trans group is preferably used as a dissolution inhibitor. The photosensitive dry film of the present invention is characterized in that the photosensitive polyimide precursor composition is applied onto a support film, and a solvent is removed, followed by lamination of the film. The flexible printed circuit board of the present invention is characterized in that it is formed using the above-mentioned 139901.doc 201006867 photosensitive dry film. The polyimine precursor of the present invention is characterized in that the ratio (Mw2/Mwl) between the weight average molecular weight (Mwl) of the varnish and the weight average molecular weight (Mw2) after desolvation of 120 ° C or less is 0.7 or more. [Effects of the Invention]

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. [Embodiment] Hereinafter, the present invention will be specifically described. (A) Polyimine precursor The single system of the polyamidene precursor uses acid dihepatic and diamine. It is known that the polyimine precursor is reduced in molecular weight due to the decrease in the molecular weight of the desolvent* accompanying heating, and the acid secondary system used for the polyimide precursor is used by the following formula (1). ) is not the acid dianhydride. If it is not the acid anhydride of the structure, then |

^Individual use' can also be used in combination with two or more types. The use of the anti-solvent step in the use of the anti-solvent step can reduce the amount of I to 4 in the bending of the dry film of the salted umbrella, and can improve the bending. Folding. [Chemical 6]

139901.doc (1) 201006867 (X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms. The core represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 10, an alkoxy group, or a halogen group. In the above, from the viewpoint of the decrease in the molecular weight in the self-inhibiting solvent removal step, it is preferred to use an acid dianhydride represented by the following formula (3). [Chemistry 7]

❹ ❿ P (3) j 0 (a is an integer of Tables 7F1 to 20. b represents an integer of 3 to 3 。. & represents a nitrogen atom or a monovalent alkyl group having a carbon number of 1 to 10) by the above formula (3) In the Junji liver expressed by a, a is better than (4) is 5Λ20. Specifically, it can be mentioned: butanediol-meta-trimellitic acid=one fermentation-bi-p-trimellitic anhydride, heptanediol·bis-p-trimellitic acid=hepatic sterol trimellitic acid (four), second generation two Alcohol·bis-p-trimethylene benzoate-t-propanol-bis-p-stacked tris-acetic anhydride vinegar, poly 1,4·butanediol·manic anhydride S曰 special. These compounds may be used alone or in combination. 』J will use 2 other needles in the polyimide precursor of 2 months. Star _ and ^ Jiangman - Xuan, can also be cited: homobenzene... As aromatic tetradecanoic acid, can be listed II, 3,3,,4,4, · biphenyltetracarboxylic acid, liver, 2,3, 3,4'-biphenyltetracarboxylic acid-wm acid anhydride, 2,2,3,3,-biphenyltetracarboxylic acid-liver 3,3,,4,4, dimethane-formic acid anhydride, tetracarboxylic acid - wild, 2, 2, 3, 3, 2 stupid 139901.doc 201006867 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, double (3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) fluorene, 3,3·-oxygen Diphthalic dianhydride, 4,4,_oxydiphthalic acid two-needle, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 13-di-argon-i ,3-dioxy-5-isobenzofurandecanoic acid-1,4-phenylenedicarboxylate, 4-(2,5-dioxotetrahydrofuran-3-yl)_1,2,3,4-tetrahydronaphthalene _ 1,2-Dicarboxylic anhydride, 1,2,5,6-naphthalene tetracarboxylic acid two-needle, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine tetra Diacetate, 3,4,9,1〇-indole tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane needle 2,2-bis(4-(3,4- Iso-phenoxy)phenyl)hexafluoropropanil-dissolved liver, 2'2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane dianhydride, 2,2 - bis(trifluoromethyl)_4,4,_bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, ethylene glycol-trimellitic anhydride, and the like. Examples of the aliphatic tetracarboxylic dianhydride include cyclobutane tetracarboxylic dianhydride, cyclopentane tetraphthalic acid dianhydride, 2,3,5,6 cyclohexanetetracarboxylic dianhydride, and 5_(2,5_ Dioxotetrahydrofuranyl-3-indolyl-3-cyclohexene-1,2-dicarboxylic acid di-hepatic, bicyclo[: 纠 ^ 稀 - - such as fine formic acid two needle ~ from butyl: tetracarboxylic dianhydride. From the viewpoint of lowering the warpage after baking, the acid: = is used in the range of the total amount of the acid dianhydride of the polyimide precursor, preferably from the ear to 5 〇 mol%. And: = the diamine of the polyimide precursor, the viewpoint of the reduction of the knives in the step of suppressing the solvent removal, and the high viscosity of the solvent after the solvent removal; I, the ruthenium film is considered, compared It is preferred to use 139901.doc 201006867 diamine represented by the following formula (2). The diamines represented by the above structures may be used singly or in combination of two or more. In the following formula (2), r2 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. & represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 10, an alkoxy group, or a dentate group) Illustrative. Bis(2-aminobenzoic acid) Ethylenedihydrate, bis(3-aminobenzoic acid) ethylene diester, bis(4-aminobenzoic acid) ethylene diester, bis(2-aminobenzoic acid) ) 1,3_propylene diester, bis(3-aminobenzoic acid} 1,3_propylene diester, bis(4-aminobenzoic acid) 1,3-propane diester, bis(2-amino group) Benzoic acid}1,4-butane diester, bis(3-aminobenzoic acid) 1,4-butane diester, bis(4-aminobenzoic acid)•butylate, bis(2-aminobenzoic acid) 3-methyl-I,4-butanediacetate bis(3-aminobenzoic acid) 3-methyl-1,4-butanediester, bis(4-aminobenzoic acid) 3-methyl", oyster Butane diester, bis(2-aminobenzoic acid) 1,5-pentane, bis (3-aminobenzoic acid: diester, bis(4-aminophenylphthalic acid) 1,5-pentane diester , bis (2_amino-based acid formic acid 1 〇癸 diester, bis(3-aminobenzoic acid) 1,1 〇 癸 癸 vinegar, acid) 1,10-decane diester, etc. Used alone, more than one species. Bis(4-aminobenzamide) Can be used at the same time 2, further, soldiers / τ, ~ the amount of knives decreased, and the solvent to improve the viscosity of the photosensitive dry film test 139901.doc 201006867 care, it is better to use a compound represented by the formula (4).

(Z is an alkylene group having 2 to 20 carbon atoms. I represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 1 Torr, an alkoxy group, or a halogen group. c represents an integer of 2 to 3 Å) For example, polyoxymethylene_di-o-amino benzoate, polyoxymethylene-di-m-amino benzoate, polyoxymethylene-di-p-amine Benzobenzoate, polyoxytriazinyl-bis-o-aminobenzoic acid 8曰, polyoxymethylene-di-m-aminophenylphthalate, polyoxymethylene-di-p-amino group Benzoate, polyoxytetramethylene-di-o-amino benzoate, polyoxytetramethylene-di-m-aminophenyl phthalate, polyoxytetramethylene-mono-p-amine Benzoate, polyoxy-3-indolyltetradecylene-di-o-aminobenzoate, polyoxy-3-methyltetramethylene-di-amino-m-phenyl benzoate, polyoxidation 3-mercaptotetrakisinyl-di-p-aminobenzoic acid ester, polyoxypentaethylene-di-o-amino benzoate, polyoxypentaethylene-di-m-moon female Formate, polyoxypentamethyl_di-p-aminobenzoate, polyoxydecainyl-di-o-aminobenzamide Ester, polyoxymethylene-di-m-amino benzoate, polyoxymethylene-di-p-aminobenzoate, poly(tetradecyl/3-methyltetramethylene) Ethyl ether) diol bis(4-aminobenzoate) 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 diamines are adjusted to 139901.doc -12· 201006867 by 25 mo: to 22:. (4) The diamine represented by all the diamines is particularly preferably a compound represented by the above formula α. ϋ -ν (αλ^· ± ) kg and a compound represented by the above formula (4) Use with ^ ^ A 。. The compound represented by the above formula (2) and the If opened by the above-mentioned compound (Μ, D±^, and the formula (4) are used to reduce the distortion and de-rolling ^ Omega turbulence, the viscosity of the photosensitive dry film after the mixture is improved, and good lithographic properties are considered by the above formula (4)

The compounding amount of the compound represented is better than that of the summer, and is 25 mol% to 75 mol% with respect to the total amount of the diamine. Further, the above diamine can be used together with a diamine other than the above. Specific examples thereof include 1,4-diaminobenzene, i,3-diaminobenzene, 2,4-diaminotoluene, 4'4'-diaminodiphenylmethane, M, and diamine. Diphenyl ether, diaminodiphenyl ether, 3,3^ dimethyl-4,4,-diaminobiphenyl, 2,2,-dimethyl-4,4,diaminobiphenyl , 2'2,-bis(trifluoromethyl)_4,4.diaminobiphenyl, 3,7-diamino-dimercaptothiophene_5,5-dioxide, 4,4 , _diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4,_bis(4-aminophenyl) sulfide, 4,4'-diaminodiphenyl Sulfone, 4,4,-diaminobenzidine, in-bis(4-aminophenoxy)alkane, 1,3-bis(4.aminophenoxy)_2,2-dimethyl Propane, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl)anthracene, 5(6)-amino group·1_ (4-aminomercapto)-1,3,3-trimethylindan, 1,4-bis(4-aminophenoxy)benzene, anthracene-bis(4.aminophenoxy)benzene , bis-(3-aminophenoxy)benzene, 4,4,_bis(4-aminophenoxy)biphenyl, 44,_bis(3-aminophenoxy)biphenyl, 2, 2-bis(4-aminophenoxyl) Phenyl)propane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 139901.doc •13- 201006867 2,2 - bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3,3,-disulfoyl-4,4,-diaminodiphenylcarbamate, 4,6-di 1,3-phenylenediamine, 3,3,-di-diyl-4,4'-diaminobiphenyl, 1,4-bis(4-aminophenoxy)pentane, 15 pairs ( 4,_Aminophenoxy)pentane, bis(γ-aminopropyl)tetramethyldioxanthene, 14_bis(γ-aminopropyldimethylmethylalkyl)benzene, bis(4- Aminobutyl) tetradecyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, a diamine oxime compound represented by the following formula, and the like. These may be used alone or in combination of two or more. From the standpoint of lowering the warpage after baking, it is preferred that the diamines are blended with % to 50 moles per mole relative to the total moles of diamine. [化10]

When α is 5 olefinized oxime, the polyamine precursor can be blocked by using 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 acetified by using a well-known compound such as an alcohol compound and a method. The polyimide precursor of the present invention can be prepared into a photosensitive polyimide intermediate composition by blending a sensitizer and an organic solvent. (B) Photosensitive agent The photosensitive polyimine precursor composition of the present invention is formulated as a sensitizer by compounding an acid by irradiation with active light. The sensitizer is not particularly limited as long as it generates an acid by irradiation with lingual light, and the sensitizer is preferably 139901.doc -14-201006867. The awkward diazide compound or the naphthalene-containing diazide compound contains The hydration of the diazide structure can be used, for example, in the specification of U.S. Patent No. (7) m 3 and U.S. Patent No. 3,669,658. Among them, it is preferred to use a compound of sulphuric acid with ls2-naphthalene-2·diazide acid or 1>2 broccoli-2_disodium-5-«. These may be used alone or in combination of two or more.

The amount of the sensitizer to be used in the present invention is preferably from 5 parts by mass to 35 parts by mass, more preferably from 1 part by mass to 30 parts by mass, per part by mass of the ruthenium imine precursor. The amount of the sensitizer is preferably 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 considered to be good from the viewpoint of sensitivity and presentation of the coating layer (IV). It is 35 parts by mass or less. (C) The organic solvent 'for example, N-methyl, hydrazine, hydrazine dimethyl acetamide, γ 2-«pilotidine _, N, N dimethyl in the organic solvent used in the invention Carbamide butyl vinegar, dimethyl sulphate. χ, if necessary, the solvent can be adjusted to be lower than the solvents of the solvents. The 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, methylethethenone, and methyl isobutyl ketone, and ethanol, isopropanol, n-butanol, ethanol, monoethylene glycol, and triethylene glycol. An alcohol such as propylene glycol or hexanediol, I〆dioxane, trioxane, diethyl acetal, 1,2-dioxolane, diethylene glycol dioxime ether, tetrahydrofuran, benzoin ether, three Ethers such as ethylene glycol dimethyl ether, ethyl acetate, methyl benzoate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate S曰, ethylene glycol monopropyl ether acetate, ethylene Alcohol diacetate, propylene II 139901.doc •15- 201006867 Fermented monoterpene ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propanol monobutyl ether acetate, propylene glycol II Esters such as acetate, diethylene glycol monoterpene ether acetate, monoethylene glycol monoethyl ether acetate, diethylene glycol diacetate, n-heptane, n-octane, cyclohexane, benzene , such as toluene, xylene, ethylbenzene 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 polyimine. If the amount is more than 9 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 can be optionally provided 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. As a compound having a group which hydrogen-bonds to a carboxyl group or a phenolic hydroxyl group, T is a decanoic acid compound, a tarenic acid ester compound, a guanamine compound, an adenoid compound, and the like. The compound represented by the following general formula (6) is more preferably a guanamine compound or a urea compound from the viewpoint of the dissolution inhibiting effect and the storage stability in the developer containing the aqueous alkaline solution. 139901.doc 201006867 [Chem. 11]

(6) (m represents an organic group containing all or a part of a carbon atom, a nitrogen atom, a halogen atom, or a sulfur atom. The rule 5 and & may be the same or different) ❿ As the guanamine compound, for example, Ν, Ν ^Ethylethyl _ > Ν, Ν-diisopropyl decylamine, hydrazine, hydrazine dimethyl decyl decylamine, hydrazine, hydrazine _ dibutyl ethanoamine, hydrazine, hydrazine _ dipropyl propyl Amine, __dibutylformamide, hydrazine, hydrazine = ethyl propyl amide, hydrazine, hydrazine dimethyl propylamine, hydrazine, hydrazine, • dimethoxy _ν, ν, _ dimethyl grass Indoleamine, hydrazine. methyl _ ε. caprolactam, 4 _ phenyl phenyl stearamine, salicylamine, salicylate, alum, 7 ^ armamine, acetophenone, 2, - hydroxyethyl anilide, 3 ·- phenyl aniline, 4, hydroxy phenyl aniline. Preferably, it is preferred from the viewpoint of the low glass transition point of the film obtained by baking the photosensitive layer, (4) the solubility in the coating (4) of the inclusive aqueous solution, and the high residual rate. It is a compound having an aging base, and more preferably a guanamine compound having a phenolic hydroxyl group. Specifically, it can be as follows: 4. 4 (4) benzyl phenylamine, 2'. phenyl aniline, 3, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ These may be used singly or in combination of two or more. Examples of the urea compound include dimethyl urea, tetramethyl urea, tetraethyl urea, 13'-based urea, and 3-hydroxyphenyl urea. Wherein, the solubility in the developing solution containing the alkaline water & /liquid mixture, the high residual film rate, the photosensitive layer, and the film obtained by baking the photosensitive layer by the plate &#β, ' Low glass transfer 139901.doc •17· 201006867 Point of view, better is a urea compound containing a phenolic hydroxyl group. Specifically, s can be exemplified by 3-hydroxyphenylurea. 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 with respect to the carboxyl group of the polyimide precursor and the phenolic hydroxyl group of 1 mol from the viewpoint of exhibiting a dissolution inhibiting effect.丨 to 〇m〇i, it is better to mix 0.15 mol to 1.5 mol. In the case of using a urea compound, the dissolution inhibitor of the present invention is preferably a ruthenium of a polyethylenimine precursor and a phenolic hydroxyl group of 1 mol from the viewpoint of exhibiting a dissolution inhibiting effect. From 2 〇m〇h, from the viewpoint of exhibiting dissolution inhibition effect and exhibiting the toughness of the resin obtained by baking, it is 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 and the phenolic hydroxy group of the polyimide precursor, from the viewpoint of the dissolution inhibiting effect. It is preferably in the range of 0.1 mol to 1.5 mol. (E) Discrete compound The photosensitive polyamidiamine precursor composition of the present invention may optionally contain a phenol compound. 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 general structure (as a component which is not equivalent to the dissolution inhibitor of the present application). 139901.doc •18- 201006867 [Chem. 12]

Y

(7) (R7 and Rs each independently represent a hydrogen atom or an organic group containing a carbon atom of i to 5 Å and an oxo sulfonium to 1 (). X independently represents a hydrogen atom or an organic group having a base or a carbon number of 1 to 20. Base) [Chem. 13], R9-R!

R 11 (8) (R9 and Rn each independently represent an organic group having a carbon number of 丨 to 6, and Riq represents a bonding group or an organic group having 1 to 20 carbon atoms) Specifically, dihydroxydiphenyl fluorene is exemplified. Alkane, 4,4,-oxydiphenyl phenol, anthracene, 4-bishydroxyphenoxy), 1,3-bis(4-hydroxyphenoxy)benzene, 1,5-bis(o-hydroxybenzene) 2 nucleus such as oxy)_3_oxapentane, hydrazine 1, hydrazine 1, bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, tris(hydroxyphenyl)methane, tri Hydroxyphenyl)ethane, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]_α, α-didecylbenzyl} phenanthene and the like 3 nucleus 'from the following structural formula (a) to a polynuclear body represented by the structural formula (h). These phenol compounds may be used singly or in combination of two or more. 0 139901.doc -19- 201006867 [Chem. 14]

The compounding amount of the desired 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 part by mass of the polyimine precursor. If the amount is less than i part by mass, it is difficult to suppress the sensitization of the photosensitive dry film obtained after the solvent removal step if the solubility in the solution of the solution is more than 3 parts by mass. The layer becomes brittle. (F) Plasticizer The photosensitive polyimine precursor composition of the present invention is also used as a plasticizer by using a compound represented by the following formula (9). 13990l.doc -20- (9) 201006867 [Chem. 15]

Rl3

(Foot 12 to 1114 is an organic group containing an ethylene glycol chain and/or a propylene glycol chain, and may be the same or different) Specific examples thereof include compounds represented by the following structural formulae (i) and (j). However, it is not limited to this. Further, these compounds may be used singly or in combination of two or more. [Chemistry 16]

(d is an integer of 0 or more, and e is an integer of 0 or more) The amount of the plasticizer of the present invention is preferably 1 part by mass relative to the mass of the polyamidene precursor 100 139901.doc -21 - 201006867 The amount is preferably 30 parts by mass, and further preferably i parts by mass to 1 part by mass. When the amount is more than i part by mass, the effect of the surface curvature is reduced, and if it is 30 parts by mass or less, the desired pattern is obtained without adversely affecting the developability. (G) Crosslinking agent 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 (1), a polyfluorene imine precursor represented by the following formula (1) or A carboxyl group-containing polyimine precursor ester compound. [化17] °

Ri6〇〇C\ /COOR19

/R1S r17ooc, coor18 (10) is a tetravalent organic group, a core 6 to a heart 9 series hydrogen or a monovalent organic group having a carbon number of 1 to 2, which may be the same or different) [Chemical 18] 0 0 oo R25 〇OC\ / yRa>/ \ λ RmOOC coor27 \/

H

H

N«23—N R28〇〇C coor, g fC〇〇Rj /R24 D / \ R30OOC COOR5 (11) (ho, R22 ' R24 is a tetravalent organic group, which can be the same or different. hi, R23 2 The valence organic group may be the same or different. The 25-foot 32 hydrogen or the 1-valent organic polymer having a carbon number of 1 to 20 may be the same or different. g is an integer from 0 to 100. From the viewpoint of the effect, the amount of the crosslinking agent of the present invention is 139901.doc • 22-201006867 The molar number of the residual amine group relative to the polyimide precursor is preferably 0.1 mol to 1.5 mol, more preferably It is 〇·5 moli i丨m〇1. The residual amine amount can be calculated by high performance liquid chromatography. (H) Thermal test agent The photosensitive polyimine precursor composition of the present invention may contain a thermal test agent 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 a salt such as a sulfonic acid, protecting it with a dicarbonate compound, and protecting it with a helium compound. Therefore, it is stable without being alkaline at room temperature, and can be deprotected by heating to prepare a thermal test agent for producing the test. Further, the baking temperature of the polyimide precursor can be set to a relatively low temperature by blending the thermal 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)·2,6- A compound in which dimercaptopiperidine or an amine group of an aromatic diamine is protected by dibutyl dicarbonate or the like. Among these, from the viewpoints of storage stability of the photosensitive polyimide intermediate composition, molecular weight stability of the solvent, solubility, and ion mobility, Ν_(isopropoxycarbonyl group is preferred. -2,6-Dimethylpiperidine, Ν-(t-butoxycarbonyl)_2,6-dimethylpiperidine, Ν-(benzyloxycarbonyl)-2,6-dimercaptopiperidine a compound in which the amine group of 4,4-diaminodiphenyl ether is protected by dibutyl dicarbonate, and the amine group of 3,4,-diaminodiphenyl ether is protected by dibutyl dicarbonate, Bis-aminobenzene 139901.doc -23- 201006867 oxy) a compound of the present invention protected by dicarbo-dibutyl acetonate, an amine of 1,3-bis(4-aminophenoxy)benzene a compound protected by dibutyl dicarbonate, a compound of bis(4-amine basic formic acid), i.e., 3-aminodiamine, which is protected by dibutyl glycolate, 1,4-bis(4-amino group) A compound in which the amine group of phenoxy)pentane is protected by dibutyl phthalate. This compound can be synthesized, for example, by a well-known method described in Chmistry Letters Vol. 34, No, 10 (2005). The amount of the thermal test agent of the present invention is preferably from 0.5 part by mass to 30 parts by mass based on 1 part by mass of the polyamidene precursor, from the viewpoint of the promotion of the imidization and the development performance. More preferably, 〇 5 parts by mass to 2 〇 ®® parts. (I) Phosphate ester compound The phosphoric acid ester compound may be optionally added to the photosensitive polyimide intermediate precursor 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 formula (丨2), the following formula (13) or the following formula (14) is used. R33——Ο——P——〇—R35 I (12) Ο (R33 to R) indicates an organic group having a carbon number of 1 or more, which may be the same or different) 139901.doc -24· (13) 201006867 [Chem. 20]

They may be the same or not (R36 to R39 represent an organic group having a carbon number of 1 or more) [Chem. 21]

(wherein Rm is hydrogen or a monovalent organic group), in consideration of improving the flame retardancy and plasticity of the photosensitive polyimideimine precursor composition, the ruler to the ruler 35 of the above formula (12) or the above R36 in the formula (13) is preferably selected from the group consisting of methyl, ethyl, butyl, 2-ethylhexyl, butoxyethyl, phenyl, tolyl, dimethylphenyl, aminobenzene Further, in the case of considering the thermal stability and the warpage improving effect of the photosensitive dry film, it is preferable that the above formula (14) is selected from the group consisting of hydrogen, dihydroxy stupyl and dibutyl. An organic group having a base group and an organic group containing a (meth)acrylic acid vine group. Further, it is preferable to consider the compatibility with the resin varnish or the warpage improving effect at the time of photosensitive dry film formation. Hydrogen. 139901.doc -25- 201006867 These disc acid compounds can be formulated individually or in combination of two or more. The ratio of the phosphate compounds is better than that of the mass parts. Further, i parts by mass to 2 parts by mass. If the amount is more than i parts by mass, plasticizing property is exhibited, and if it is 3 〇 mass In the following, the portion of the photosensitive polyimide intermediate composition that is not irradiated with the active light is hardly eroded in the developer containing the aqueous test solution. A good radiation image can be obtained. (J) Organic phosphorus compound The photosensitive light of the present invention The organophosphorus compound represented by the following formula (15) can be blended in the polyimine precursor composition, and the resin pattern obtained by baking can be imparted with flame retardancy by blending the organic filler compound. [化22] -R 41

(15) ι \

IN «41 (R/n 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 SO part by mass, and more preferably from 3 parts by mass to 25 parts by mass. . When the blending amount is 5% by mass or more, the flame retardancy is exhibited, and if it is 3 parts by mass or less, the resin pattern obtained after baking becomes tough. (K) Other components The photosensitive polyimine precursor composition of the present invention may be formulated with a rice compound, a tris-salt compound, a tetra-salt compound, or a sulfur-compound as needed. The adhesion to the copper substrate can be improved by blending the compounds. 139901.doc 201006867 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 〇. 丨 by mass or more, the adhesiveness is improved. When the amount is less than 1 part by mass, 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, a yeast such as ethanol, 2-propanol or ethylene glycol, ethyl lactate or benzene may be blended as needed. Ethyl formate, ethylene glycol monopropyl ether acetate, vinegar and other esters such as ketones such as mercaptoethyl ketone and decyl isobutyl ketone; ethers such as n-butyl ether, tetrahydrofuran and dioxane; Ether ethers such as diethyl ether and propylene glycol. 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. (Polymerization of Photosensitive Polyimine Precursor Composition) The photosensitive polyimide intermediate precursor composition of the present invention utilizes spin-mixing by blending the above-mentioned polyimine precursor and various compounds in a suitable φ container The device, the non-foaming kneader, the tri-motor equipped with the stirring blade, and the like are stirred until completely dissolved. (Production 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. 11 (1) A method in which a photosensitive polyimide film precursor composition is applied onto a film substrate, followed by solvent removal to prepare a photosensitive dry film 139901.doc • 27-201006867 Photosensitive dry film system The photosensitive polyimide precursor composition is applied onto a support film (film substrate), and the solvent is dried to form a photosensitive layer. As the support film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene/ring:ene copolymer, or the like can be used. The support film may be subjected to surface treatment for the purpose of controlling the wettability of the photosensitive polyimide precursor composition or the peeling property of the photosensitive layer obtained from the photosensitive polyimide intermediate composition. . Examples of the surface treatment method include corona treatment, frame treatment, plasma treatment, surface modification using polyoxin or an alkyd resin or an enone resin, and the like. Further, in consideration of coatability, adhesion, rollability, strength (four), cost, and the like, the thickness of the carrier film is usually 15 μη ^ 1 〇〇 _, preferably Η哗 to μ μιη.

2 light! The coating of the polyimide polyimide precursor composition can be applied to the above-mentioned support film t-coating gravure coater or gravure roll coater, doctor blade (c〇_) :: machine, lip coater, The slit extrusion coater method is carried out. 4 < Desolvation can be carried out by solvent drying (using a hot air drying or a far infrared ray, a near infrared ray dryer & A, 'dryer). From the viewpoint of the decrease in the molecular weight of the drying temperature, it is preferable that the temperature is scratched and the qualitative property is lowered. The social stability of C to 20C from the sensitizer is considered to be 5 〇. 〇 to i 1 〇. The film thickness of the photosensitive layer #" ^ c ° is obtained by removing the solvent from ε _ 、 , preferably from 5 μηι to 100 μπι, more preferably from β to 50 μπι. From the viewpoint of the insulation reliability of the above-mentioned 疋5 μηι, the film thickness is lower than the pregnancy μ θ 100 μηι from the viewpoint of obtaining a good weight (4) 疋 5 μΓη 1〇π radiation image. The preferred order of the ruthenium is between the weight average of the 139901.doc -28-201006867 sub-quantity (Mwl) and the weight average molecular weight (Mw2) after desolvation below 120 的. When the ratio (River 2/]^1) is 〇7 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 a photosensitive dry film to form a photosensitive build-up film. The adhesion of the photosensitive layer to the support film can be prevented by laminating the film. As the covering crucible, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene/cyclodecene copolymer can be used. ' ^ (2) A step of forming a photosensitive layer by pressure-bonding a photosensitive dry film on a substrate on which a pattern is placed, and superimposing the photosensitive dry film on a surface on which a circuit such as an FPC is formed (a substrate on which a pattern is arranged) is used. A method known in the art for flat lamination or roll lamination, vacuum pressing, etc., from 4 (TC heating to 130, preferably from 6 〇 t: heating to 120 C, using a pressure of 0.2 MPa to 5 MPa on one side) Lamination (pressure bonding) is carried out, whereby the photosensitive layer can be laminated. φ At this time, 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 pressing temperature is 4 (rc or more, it does not cause trouble due to adhesion when the position is aligned before lamination, and by laminating the laminating temperature to 13 (TC or less, laminating without sensitizing agent can be laminated) Furthermore, the laminable temperature means that there is no problem such as residual bubbles, and the film 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. The viscosity of the glass is transferred to the photosensitive layer (hereinafter T g) laminating temperature may be suitable for lamination of photosensitive dry film. After lamination of photosensitive layer, 139901.doc •29· 201006867 support film peelable or x touchless a ” no peeling. When 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 fine pores or fine width lines, the photosensitive layer is exposed by a mask having an arbitrary pattern. The amount of exposure varies depending on the photosensitive polyimide precursor precursor H. 'It is usually 1 〇〇, just ^^2. As the active light used at this time, for example, an n-line or an electron beam rabbit can be cited. As the light source of the active light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an i-lamp, etc. can be used. In the present invention, it is preferable to use an i-ray of a mercury lamp (365 (four), h-ray (10) nm), g Radiation (436 nm). The method of irradiating the active light may be either a close exposure or a projection exposure. (4) A step of developing with an aqueous alkaline solution, after exposure, using a developing solution, using a dipping method, a spray A radiation image can be obtained by a well-known method, and as the developer, an aqueous solution of an aqueous solution of sodium hydroxide, a water-based solution, a carbon-water solution, a carbonated carbon solution, or a tetramethylammonium hydroxide aqueous solution can be used. In the step, it is preferred to carry out the heating-surface development on the surface of 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 such viewpoints, the developer The temperature is preferably from 20 ° C to 60 ° C, and further preferably from 25. 〇 〜 5 〇. 〇. (5) rinsing step using at least one solvent selected from the group consisting of water and an acidic aqueous solution. Use well-known methods such as dipping method, spray method, etc. 139901.doc • 30- 201006867 t = for the rinsing liquid, water or organic solvent can be added to the water. It is preferred in this step to maintain the rinsing liquid at a suitable temperature. Thereby, the residue on the substrate or the resin can be removed after development. As the temperature of the rinsing liquid, from the viewpoint of removing the residue, it is preferably 15t to 6 (the rc is preferably the intermediate washing liquid after washing, and the inorganic acid aqueous solution or the organic acid aqueous solution can be washed. As the no (four) (four) liquid Specific

5 can be exemplified by 1 acid water reduction, (10) water μ, glycerin aqueous solution, and aqueous solution. Specific examples of the organic acid aqueous solution include a formic acid aqueous solution, an acetic acid aqueous solution, an aqueous citric acid solution, a lactic acid aqueous solution acid aqueous solution, or an organic acid aqueous solution. The cleaning time is preferably from 5 seconds to 12 G from the viewpoint of self-cleaning efficiency. Seconds, and thus better, leap seconds to 6 seconds. 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 the active light After the rinsing step, the entire surface of the obtained radiation image is irradiated with the active light. The time of the subsequent curing step can be shortened by the decomposition of the sensitizer. Further, the light transmittance of the resin pattern obtained after the curing step can be improved. Further, with this step, the residual stress applied to the substrate and the photosensitive layer derived from the photosensitive agent can be reduced, and the curvature of the multilayer printed circuit board obtained in the resin pattern forming step can be reduced, and the folding endurance can be improved. The amount of exposure to be irradiated in this step varies depending on the type of the sensitizer used or the thickness of the photosensitive layer, and is usually from 100 mJ/cm 2 to 3 〇〇〇 mJ/cm 2 . For example, when the sensitizer is a naphthoquinone diazide compound and the film thickness of the photosensitive layer is 25 μηι 139901.doc -31 - 201006867, it is preferably mj/em2 or more from the viewpoint of photolysis of the sensitizer. Examples of the active light rays used at this time include a ray line, an electron beam, an ultraviolet ray, and a visible gaze. As the light source of the active light, a low-pressure mercury lamp, a high-pressure mercury lamp, a silver lamp, a super-pressure mercury lamp, a halogen lamp, or the like can be used. Among these, the better county “Μ 乂 乂 疋 疋 疋 疋 疋 疋 疋 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Active light. From the viewpoint of workability, the heating temperature is preferably 30° (: to 130 〇, and it is good to serv it to 丨 (10). (7) Baking at 100 to 40 (TC) The step of baking the radiation image obtained in the above step, thereby forming a resin pattern. The baking is performed at 1 Torr (TC to 40 (continuous or staged at a temperature of rc for 5 minutes to 5 hours. Then, It is made into a processed product. In the case of Fpc, it is preferable to cure it from the viewpoint of preventing oxidation of wiring, and it is preferable to cure it in a temperature range of 2 〇〇 ° C. The product 'is an FPC, a multilayer printed circuit board, etc. [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, but it is not limited to these examples. (Synthesis of Polyimine Precursor) Synthesis Example 1 Synthesis of Polyimine Precursor (i) Addition to a two-neck separable flask 6.4 g of l,3-bis(3-aminophenoxy)benzene, 62 g of γ-butyrolactone, stirred until a homogeneous solution was obtained. Then, 10 g of pentanediol-bis-trimellitic anhydride was added. The ester was stirred while being cooled in an ice bath for 1 hour, and then stirred at room temperature for 6 hours. Then, the 139901.doc -32-201006867 product was subjected to pressure filtration through a 5 μηη filter to obtain a poly-imine. Precursor (i). The molar ratio of the acid dianhydride to the diamine, the solid content and the weight average molecular weight of the polyimine precursor (i) solution of the obtained polyimine precursor (1) are shown in Table 1. Synthesis Example 2 Synthesis of Polyimine Precursor (Π) To a three-neck separable flask, 4.8 g of 1,3-bis(3-aminophenoxy)benzene and 6.8 g of polyoxytetrazide were added.曱-di-p-amino benzoate and 82 g of γ-butyrolactone are stirred until they become a homogeneous solution. Then, i 二醇 g 之 二醇 二醇 双 双 双 双 双 , Stir for 1 hour while cooling in an ice bath. Then, stir at room temperature for 6 hours. Then, pressurize the product with a filter of 5 μηι. And obtaining a polyimine precursor (丨丨). The molar ratio of the acid dianhydride to the diamine of the obtained polyimide precursor (ii), and the solid solution of the polyimide precursor (ii) solution The fractions and the weight average molecular weights are shown in Table 1. Synthesis Example 3 Polyimine imine precursor (iii) Synthetic reaction Two-neck separable flask was charged with 9.7 g of 1,3-bis(3-aminobenzene). Oxy)benzene, 13.7 g of polyoxytetradecylidene-di-p-aminobenzoate, 168.8 g of γ-butyrolactone' was stirred until it became a homogeneous solution. Then, 10 g of pentanediol was added. - Bis-trimellitic anhydride ester, 115 g of decanediol_bis-p-trimellitic anhydride ester, stirred while cooling on an ice bath for an hour, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (iii) was obtained by pressure filtration of the product using a filter of 5. 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 polyamidene precursor (iii) are shown in Table i. 139901.doc •33- 201006867 Synthesis Example 4 Synthesis of Polyimine Precursor (iv) To a three-neck separable flask was added 8.8 bis(3-aminophenoxy)benzene, i2.4 § polyoxidized four Methylene-di-p-aminobenzoic acid vinegar, 99.7 hydrazine-butyl (tetra), was stirred until it became a homogenate solution. Then, ίο g pentanediol-trimellitic anhydride ester and 115 g of decanediol-bistrimellitic anhydride were added, and the mixture was stirred for an hour while cooling in an ice bath, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor (iv) 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 poly(imine precursor) (iv) solution, and the weight average molecular weight of the obtained polyimine precursor (4) are shown in Table 1. Synthesis Example 5 Synthesis of Polyimine Precursor (v) To a three-neck separable flask was added 1 〇·〇g of bis(4-aminobenzoic acid) 1,3-propanediester and 13.1 g of polyoxygenated four. Methylene, di-p-aminobenzoic acid ester, 104.1 g of γ-butyrolactone was stirred until it became a homogeneous solution. Then, adding ίο g pentanediol-bis-p-trimellitic anhydride ester, ii5 g of decanediol-meta-trimellitic acid _-----ice-bath cooling-surface stirring for 1 hour, and then at room temperature Mix for 6 hours. Then, the (iv) imine precursor (7) is obtained by pressurizing the product with a filter called 5 Å. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (7) solution, and the weight average molecular weight of the obtained polyimine precursor (7) are shown in Table i. Synthesis Example 6 Synthesis of Polyimine Precursor (vi) To a three-neck separable flask was charged 9.8 g of bis(4-aminobenzoic acid), 3 propane Sa 12·9 S polyoxytetramethylene. _Di-p-aminobenzoquinone 103.1 g of γ-butyrolactone was stirred until it became a homogeneous solution. I39901.doc 201006867 Then add '10 g of glutaraldehyde-bis-p-trimellitic acid acate, Π.5 g of decanediol-bis-p-trimellitic anhydride, and let it stand for 1 hour while cooling. It was then stirred at room temperature for 6 hours. Then, the polyimide precursor (vi) was obtained by pressure filtration using a 5 μΓ filter. The molar ratio of the diuret and diamine of the obtained polyimine precursor (vi), the solid content of the solution of the polyimine precursor (vi), and the weight average molecular weight are shown in the Table. Synthesis Example 7 Synthesis of Polyimine Precursor (vii) To a three-neck separable flask, 9.5 g of bis(4-aminobenzoic acid) 1,3-propanedicarboxylate and 12-4 g of polyoxytetramine were added. The bis-di-amino benzoate, 101.0 g of γ-butyrolactone, was stirred until it became a homogeneous solution. Then 'add ίο g pentanediol-bis-p-trimellitic anhydride ester, 115 g of decanediol-bis-p-trimellitic anhydride ester, stir it on ice for one hour, then stir at room temperature 6 hour. Then, the polyimine precursor (vii) is obtained by subjecting the product to a pressure filtration using a 5 μηη2 filter, and the obtained acid dianhydride precursor (vii) and the diamine are obtained. The ear ratio, the solid content of the polyimide intermediate (vii) solution, and the weight average molecular weight are shown in Table 1. Synthesis Example 8 Synthesis of Polyimine Precursor (viii) To a two-neck separable flask was charged 9.1 g of bis(4-aminophenylphthalic acid) 1,3-propanedicarboxylate and 154 g of polyoxygenated four. The fluorenylene di-p-aminophenyl phthalate and 107.3 g of butyrolactone were stirred until they became a homogeneous solution. Then 'add ίο g pentanediol _ bis-p-trimellitic anhydride ester, 115 g of decyl alcohol-bis-p-trimellitic anhydride ester, and stir for one hour while cooling in an ice bath, 139901.doc -35- 201006867 Stir at room temperature for 6 hours. Then, the polyimine precursor (viii) was obtained by pressure filtration using a filter of 5 μηι. 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) To a three-neck separable flask was charged 9.8 g of bis(3-aminoformic acid) 1,3-propanediester and 12.9 g of polyoxytetramethylene. Base-di-p-aminobenzoic acid ester,

103 · 1 g of γ-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester, U.5 g of decanediol-bis-dimerized dicarboxylic acid liver g were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and thereafter in the chamber. Stir for 6 hours at room temperature. Then, the polyimine precursor (ix) was obtained by pressure filtration of the product using a 5 μηη transition. The molar ratio of the acid two needles 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 the Table. Synthesis Example 10 Synthesis of Polyimine Precursor (X)

To a two-neck separable flask, 9.8 g of bis(4-aminobenzoic acid) 1,3-propane diester and 12.9 g of poly(1,4-butanediol/3-methylq, 4) were added. • Butanediol) Ether bis(4-aminobenzoate), our 7-butyrolactone, stirred until a homogeneous solution. Then, 10 g of pentanediol-bis-trimellitic anhydride vinegar and 11_5 g of decanediol-bis-p-trimellitic anhydride were added while stirring for 1 hour while cooling in an ice bath, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor 00 was obtained by pressure filtration of the product using a filter of 5 μM. 139901.doc -36- 201006867 molar ratio of the obtained polydiimine precursor (χ) acid dianhydride and diamine, solid content of the polyimine precursor (x) solution, and weight average molecular weight Shown in Table 1. Synthesis Example 11 Synthesis of Polyimine Precursor (xi) To a two-neck separable flask was added iO.lg of bis(4-aminobenzoate) 1,3-propanedicarboxylate, 133 g of poly Tetra-indenyl-di-p-aminobenzoic acid ester, 105.7 g of γ-butyrolactone was oxidized until it became a homogeneous solution. Then, 10 g of butanediol_bis-p-trimethanol anhydride, u.9 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred while being cooled in an ice bath for an hour, and then stirred at room temperature. hour. Then, the polyimide precursor (xi) 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 oxime drive (xi) solution, and the weight average molecular weight of the obtained polyimine precursor (Xi) are shown in Table 1. Synthesis Example 12 Synthesis of Polyimine Precursor (χϋ) To a two-neck separable flask, 9.8 g of bis(4-aminobenzoic acid) 1,3-propanedicarboxylate and 12.9 g of polyoxytetraester were added. The fluorenylene-di-p-amino benzoate and 110.4 g of γ-butyrolactone were stirred until they became a homogeneous solution. Then, 10 g of pentanediol-p-trimellitic anhydride ester and 14.6 g of eicosanediol-bis-p-trimellitic acid ester were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then allowed to stand at room temperature. Mix for 6 hours. Then, a polyimine precursor (χΗ) was obtained by pressure filtration of the product using a filter of 5 μηη. The molar ratio of the acid two-needle to diamine molar ratio, 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. 139901.doc •37- 201006867 Synthesis Example 13 Synthesis of Polyimine Precursor (xiii) 98 g of bis(4-aminobenzoic acid) 1,3-propanedicarboxylate, 12.9 was added to a three-neck separable flask. G, polytetramethylene di-p-aminobenzoate, 123.9 g of γ-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of pentanediol·bis-p-trimellitic anhydride ester and 2〇4 g of polypropylene glycol-p-trimellitic anhydride were added, and the mixture was stirred for one hour while cooling in an ice bath, and then the mixture was stirred at room temperature. hour. Then, the polyimine precursor was obtained by subjecting the product to a pressure of 5 μm of a transition vessel. Table 1 shows the molar ratio of the acid dioxan to diamine, the solid content of the polyamidene precursor (xiii) solution, and the weight average molecular weight of the obtained polyamidene precursor (xiii). Synthesis Example 14 Synthesis of Polyimine Precursor (xiv) To a two-neck separable flask, 9.4 g of 1,3_bis(3-aminophenoxy)benzine and 73 g of γ-butane S were added. The purpose is to carry out the mixing until it becomes 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, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor (xiv) was obtained by pressure filtration of the product 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 (χν) To a three-neck separable flask, 7.1 g of 1,3-bis(3-aminobenzone) stupid and 64.3 g of γ-butyrolactone were added. Stir until it becomes a homogeneous solution. Then, 10 g of ethylene glycol-bis-p-benzoic acid ester was added and cooled in an ice bath 139901.doc _ _ _ . 201006867 One side was mixed for 1 hour, and then stirred at room temperature for 6 hours. Then, the polyimide precursor (XV) is obtained by pressure filtration of the product using a filter of 5 μη! ° The obtained acid dianhydride precursor of the polyimine precursor (χν) and the diamine The solid content of the molar ratio, the polyimide intermediate (xv) solution, and the weight average sub-quantity are shown in Table 1. Synthesis Example 16 Synthesis of Polyimine Precursor (Xvi) To a two-neck separable flask, 2·7 g of 1,3-bis(3-aminophenyloxy)benzene and 26.3 g of polyoxygen oxide were added. The fluorenylene-di-p-amino benzoate, 91 g of γ-butyrolactone was scrambled 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, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor (xvi) was obtained by pressure filtration of the product 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 (?νί) are shown in Table 1. Synthesis Example 17 Synthesis of Polyimine Precursor (χνπ) To a three-neck separable flask, 2 〇§丨, 3_bis(3_aminophenoxy)benzene, and 19.9 g of polyoxytetramethylene were added. The bis-di-amino benzoate, 74.4 g of γ-butyrolactone, was stirred until it became a homogeneous solution. Then, 10 g of ethylene glycol-bipartic acid tricarboxylate was added, and the mixture was stirred for 1 hour while cooling in an ice bath. Thereafter, the mixture was stirred at room temperature for 6 hours. Then, the polyimine precursor (xvii) 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 (xvii) solution, and the weight of the obtained polybendimimine precursor (xvii), 139901.doc •39· 201006867, the average molecular weight Shown in Table 1. (Combination of Photosensitive Polyimine Precursor 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 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 The measured polyamidiamine precursor 〇〇丨g was measured by a precision balance and dissolved in 10 g of dimethyl decylamine (and pure light) Manufactured by the Pharmaceutical Industry Corporation). The solution was passed through a 10 μm transition vessel, and the molecular weight was measured by a gel permeation chromatography instrument (manufactured by Tosoh Corporation) having a tsk-GEL SUPER® (trade name, manufactured by Tosoh Corporation). 2. Determination of the weight average molecular weight of the photosensitive polyamid A-body composition coating: by placing a polysulfon film (manufactured by Unitika Co., Ltd.) on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, The polyester film was attached by vacuum suction. On the polyester film, a photosensitive polyimide intermediate precursor composition was coated using an applicator having a gap of 67 5 μm (manufactured by Pine Science Co., Ltd.). Desolvation: Desolvation was carried out at 95 ° C for 30 minutes using a dryer (SPH-201, manufactured by Espec). Molecular weight measurement: 0.01 g of a photosensitive polyimine imprint 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 μπ1 139901.doc -40·201006867 filter, and a gel permeation chromatograph (Scheme Spectrometer) equipped with TSIC_GEL SUPER HM-H (trade name 'T〇s〇h Co., Ltd.) was used. The company manufactures) Determination of molecular weight. 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 intermediate precursor composition after the solvent removal to M2. The molecular weight ratio was calculated by the following formula 1. Molecular weight ratio = M2 / M1 m _ (bending test) Coating: A polyester film (manufactured by Unitika & Seychelles) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed. The polyester film is attached. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 1 μm (manufactured by Pine Science Co., Ltd.). Solvent removal: Desolvation was carried out by using a dryer (SPH-201, manufactured by ESPEC), φ at 95 ° C for 30 minutes. Bending test: The film obtained by removing the solvent was bent by 18 ( (curl-folded) to visually observe cracking and peeling of the photosensitive layer. The case where there is no crack or peeling is referred to as 〇', and the case where cracking or peeling is performed is referred to as X. (Evaluation of warpage) Coating: The polyester film was attached by vacuum adsorption by placing a polyester film (manufactured by Unitika Co., Ltd.) on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated. On the polyester film, a photosensitive polyimide intermediate precursor group 139901.doc-41 - 201006867 was coated with an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.). Desolvation: The solvent was removed by a dryer (SPH-2®, manufactured by ESPEC) at 95 ° C for 30 minutes. Vacuum pressing: The substrate was subjected to a solvent removal step using a polyimide film (Kapt〇n EN_l〇〇, trade name, manufactured by T〇ray-DUpont Co., Ltd.) using a vacuum press (sa_5〇i, manufactured by Tester Industries, Inc.). The photosensitive dry film obtained was subjected to vacuum pressing at a pressing temperature of 1 Torr (TC, a pressing pressure of 〇5 Mpa, a vacuum of 15 kPa, and a pressing time of i minutes. Baking: using a dryer (8ΡΗ- 2 (Η 'Manufactured by Aspec Co., Ltd.), curing was carried out under the conditions shown in Table 5. Measurement of warpage: The film obtained after baking was cut to a length of 5 cm and a width of 5 cm, and after removing static electricity, the ruler was used. The warpage of ruthenium was measured. (Example 1) Evaluation of a photosensitive polyimide intermediate precursor composition comprising a polyimide intermediate and a sensitizer The polyimine precursor obtained in Examples 1 to 3 was prepared. The solution 丨〇g, the sensitizer is 2 parts by mass of the brewed diazide compound (formula 16) 0·42 g with respect to the solid content of the polyimide intermediate, and is mixed at a ratio shown in Table 2, Put in 2 〇"^ glass bottles, using a rotary mixer (MR-5, As One Shuzo) for granted stirred until homogeneous, to obtain a photosensitive polyimide precursor composition (1-3) The evaluation results are shown in Table 2. 139901.doc -42- 201006867 [of 23]

Evaluation of a photosensitive polyimine precursor composition using 3,-hydroxyethyl sulfonamide as a dissolution inhibitor 1 〇g of the polyamidene precursor solution obtained in Synthesis Examples 1 to 3 as a sensitizer In the mass fraction of the brewing imine precursor, it is a mass fraction of the brewing nitrogen compound (formula 16) 〇·42 g, and the microbial imide precursor is 12.5 mass injuring 3_preparation base B醯 〇 〇 〇 邑 邑 & & & & & & & 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表The imine precursor composition (4 to 6). The evaluation results are shown in Table 3. 139901.doc -43- 201006867 [Chem. 23]

(16) (Example 3) Evaluation of Photosensitive Polyimine Precursor Composition Using Phenol Compound 1 μg of the polyimide precursor solution obtained in Synthesis Examples 1 to 3 as a sensitizer The amount of the quinonediazide compound 〇42 g represented by the above formula (16) and 20 parts by mass relative to the polyamidene precursor is 2 parts by mass of the polyamidene precursor solid content. 0.42 g of the phenol compound represented by the above formula (丨7) was mixed at a ratio shown in Table 4, and placed in 2 〇. 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. 139901.doc 201006867 [Chem. 24]

(17) (Comparative Example 1) The photosensitive polyazide shown in Table 获得 was obtained in the same manner as in Example 1 except that the polyimide polyimide precursor solution obtained in Synthesis Examples 14 to 15 was used in an amount of 1 〇g. Amine precursor composition (10 to 11). The evaluation results are shown in Table 2. (Comparative Example 2) In addition to the polyethylenimine precursor solution obtained in Synthesis Examples 14 to 15, 1 〇 g

The photosensitive polyimide intermediate precursor compositions (12 to 13) shown in Table 2 were obtained in the same manner as in Example 2. The evaluation results are shown in Table 3. (Comparative Example 3) The photosensitive polyimine precursors shown in Table 4 were obtained in the same manner as in Example 3, except that 1 μg of the polyimide precursor solution obtained in Synthesis Examples 14 to 15 was used. Composition (14 to 15). The evaluation results are shown in Table 4. In the case where the photosensitive polyimide intermediate precursor composition is used for a cover film of a flexible printed circuit board, it is necessary to carry out microfiltration using a developing solution containing an alkaline aqueous solution 139901.doc -45· 201006867 Obtain the 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. . (Evaluation of Performance of Photosensitive Polyimine Precursor Composition) 1) Evaluation of Material Stability Coating: Polyester film was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated (Unitika Corporation) Manufacturing), vacuum-adsorbing and attaching the polyester film. On the polyester film, a photosensitive polyimide intermediate composition was coated with 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) under the conditions of 30 ° 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 1 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). The solution was filtered through a filter of 10 μm, and the molecular weight was measured by a gel permeation chromatograph (manufactured by JASCO Corporation) equipped with TSK-GEL SUPER® (trade name: manufactured by T〇s〇h Co., Ltd.). The ratio of the amount of the knife is calculated. The weight average molecular weight of the photosensitive polyimide intermediate composition varnish is M1, and the weight average molecular weight of the photosensitive polyimide intermediate composition after the solvent removal is M2. The molecular weight ratio was calculated by the following formula 1. Molecular weight ratio = M2 / M1 139901.doc -46 · 201006867 2: lithographic performance evaluation coating: by placing a polyester film (manufactured by Unitika Co., Ltd.) on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, The polyester film was attached by vacuum suction. On the polyester film, a photosensitive polyimide intermediate composition was applied using an applicator having a gap of 67·5 μϊη (manufactured by Pine Science Co., Ltd.).

Desolvation: The solvent was removed by a dryer (SPH_201, manufactured by ESPEC) at a temperature of 95 ° C for 30 minutes. Vacuum pressing. The FCCL was first washed with a 15 wt% aqueous solution of sodium persulfate. Then, using a vacuum press (SA-501, manufactured by 1 Tester Industries, Inc.), the photosensitive dry film obtained in the solvent removal step was pressed at a temperature of 10 (TC, a pressing pressure of 〇5 Mpa, a vacuum of 15 kPa, Vacuum pressing was performed under the condition of pressing for 1 minute between k. Active light irradiation: The support film of the laminate obtained in the vacuum pressing step was peeled off, and an excess pressure mercury lamp (HMW 2 〇 1 KB, manufactured by Sigma) was used, and the exposure amount was 1.5. The conditions of J/cm2 are irradiated with ultraviolet rays. The lithography: using a spray type developing machine, the developing solution is a sodium carbonate aqueous solution of i, and the developing temperature is set as the machine, and the spray pressure is G i8 Mb, and the measurement is performed until the UV irradiation unit > The time until it is completely dissolved (hereinafter referred to as a break point). Following the enthalpy, the development time is 12 times the break point, and the H is sprayed with a spray cleaner 'developed in steamed water'. Further, the cleaning was carried out for 3 seconds using a 0.2 wt% aqueous sulfuric acid solution. The lithography performance was judged according to the development time, the residual film ratio, and the shape of the pattern, and the development performance was observed. The photosensitive polyimide intermediate precursor composition having a time of 90 seconds or less is referred to as ruthenium, and the photosensitive polyimide intermediate precursor composition of more than 90 seconds is referred to as X. Residual film rate measurement: Photosensitive layer before development The film thickness was set to T1, and the film thickness of the photosensitive layer after development was set to T2, and was calculated by the following mathematical formula: Residual film rate = T2 / Tlxl 〇〇 (%)

Pattern shape: An optical microscope (ECLIPS LV100, manufactured by Nikon Corporation) was used to observe the shape of the 100 μπι circle pattern on the lithographic pattern with a clear field of view and 100 times. The person who keeps the pattern shape is denoted as 〇, and the person who changes the pattern is denoted by X. 3: Viscosity evaluation coating of the photosensitive dry film: 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 attach the polyester. membrane. On the polyester film, a photosensitive polyimide intermediate precursor composition was coated using an applicator having a gap of 67 5 pm (manufactured by Pine Science Co., Ltd.). Go 'mixture. Use a dryer (SPH_2〇1, manufactured by Espeke) to 95. (: Desolvation in the next 30 minutes. Viscosity evaluation: The adhesion of the photosensitive layer after solvent removal is evaluated by palpation. 4: Folding resistance evaluation After curing by espec company, lithography was carried out using a dryer (manufactured by SPH-201) and cured under the conditions shown in Table 5. 139901.doc •48- 201006867 Bending test : The film obtained after curing was bent (folded and folded) 丨 80 degrees to visually observe the cracking and peeling of the cover film. The case of no cracking or peeling was recorded as 〇 'The case of cracking and peeling was recorded as X 5: Warpage evaluation coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating table (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 polyimide precursor composition was applied using a spacer of 67 5 μm (manufactured by Pine Science Co., Ltd.). Desolvent: using a dryer (SPH-201, Espe Made by the company, it is carried out at 95 ° C for 30 minutes. Agent. Shinji press. Substrate using polyimide film (Kapt〇ri thousand and εν- 1, trade name, manufactured by T〇ray-DuP〇nt) 'using a vacuum press machine (sa_5〇i,

Tester Industries, Inc.) The photosensitive dry film obtained in the solvent removal step was pressed at a temperature of 1 Torr. Vacuum pressing was carried out under the conditions of 〇, pressing pressure of M·5 Mpa, vacuum of Φ 15 kPa, and 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 facial curvature: The film obtained after baking was cut to 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 : Evaluation of flame retardancy Evaluation of warpage was carried out until coating and solvent removal. Vacuum pressing only: The substrate is made of a polyimide film (Κ3ρ_购(9), commercial 139901.doc 49·201006867 'T〇ray-Dup〇nt company), using a vacuum press like a state,

Tester Industries, Inc.) 'Photosensitive dry film obtained in the solvent removal step' is pressed at a temperature of 1 G (rc, pressure (4) force 5 Mpa, vacuum 15 ^, and 1 minute between presses) Vacuum pressing on both sides of the imide film. For baking: using a dryer (SPH_2〇1, manufactured by ESPEC), curing was carried out under the conditions shown in Table 5. Flame retardancy test: obtained in the baking step The film was cut to a width of 1 em and a length of 5, and then one of the test pieces was visually observed to ignite and the fire spread over the course. The sample annihilated in the middle was recorded as the sample, and all the burned samples were recorded as X. (Example 4 to 22) Relative to a polyimine precursor solution obtained in Examples 2 to 13 1〇g 'mix various additives in the ratios shown in Table 6-1 and put them into a 20 CC glass bottle. A mixer (MR-5, manufactured by As One Co., Ltd.) was dispensed until uniform to obtain a photosensitive polyimide intermediate composition (16 to 34). Evaluation of the photosensitive polyimide precursor compositions The results are shown in Table 7-1. The doctors (Comparative Examples 4 to 7) were for the synthesis examples 16 to 17. 1 μg of the obtained polyimide precursor solution was prepared, and various additives were mixed in the ratio shown in Table 62 and placed in a 20 CC glass bottle using a rotary mixer (MR-5, manufactured by As One Co., Ltd.). The photosensitive polyimide precursor composition (35 to 38) was obtained until it was uniform. The evaluation results of the photosensitive polyimide precursor compositions are shown in Table 7-2. 139901.doc • 50· 201006867 [Table 1] Synthesis Example No. Polyimine precursor solution Acid dianhydride/diamine (Morby) Solid weight average molecular weight 1 (1) 100/100 21 wt% 80,000 2 (ii) 100/100 21 Wt% 108,000 3 (iii) 100/100 21 wt% 113,000 4 (iv) 100/91 30 wt% 41,000 5 (v) 100/96 30 wt% 78,000 6 (vi) 100/94 30 wt% 58,000 7 (vii 100/91 30 wt% 42,000 8 (viii) 100/94 30 wt% 61,000 9 (ix) 100/94 30 wt% 59,500 10 (x) 100/94 30 wt% 57,000 11 (xi) 100/94 30 wt % 58,500 12 (xii) 100/94 30 wt% 61,200 13 (xiii) 100/94 30 wt% 61,000 14 (xiv) 100/100 21 wt% 100,000 15 (xv) 100/100 21 wt% 85,000 16 (xvi) 100/94 30 wt% 65,000 17 (xvii) 100/94 30 wt% 62,000 [Table 2] Results of Example 1 and Comparative Example 1

Photosensitive Polyimine Precursor Composition Polyimine Precursor Solution Sensitizer M2/M1 Crimping Folding Example 1 Synthesis Example 1 l〇g 0.42 g 0.98 〇2 Synthesis Example 2 10 g 0.42 g 0.97 〇 3 Synthesis Example 3 10 g 0.42 g 0.97 〇Comparative Example 1 10 Synthesis Example 14 10 g 0.42 g 0.56 X 11 Synthesis Example 15 10 g 0.42 g 0.51 X

[Table 3] Results of Example 2 and Comparative Example 2

Photosensitive Polyimine Precursor Composition Polyimine Precursor Solution Sensitizer 3'-Hydroxyethylhydrazine M2/M1 Crimping Folding Example 2 4 Synthesis Example 1 10 g 0.42 g 0.26 g 0.95 〇5 Synthesis Example 2 10 g 0.42 g 0.26 g 0.95 〇6 Synthesis Example 3 10 g 0.42 g 0.26 g 0.95 〇Comparative Example 2 12 Synthesis Example 14 10 g 0.42 g 0.26 g 0.55 X 13 Synthesis Example 15 10 g 0.42 g 0.26 g 0.50 X 139901.doc -51 - 201006867 [Table 4] Results of Example 3 and Comparative Example 3

\ or Photoreactive Polyimine Precursor Zhao Composition Polyimine Precursor Solution Sensitizer Phenol Compound M2/M1 Crimping Folding Example 3 Synthesis Example 1 10g 0.42 g 0.42 g 0.92 Ο 8 Synthesis Example 2 10 g 0.42 g 0.42 g 0.95 〇9 Synthesis Example 3 10 g 0.42 g 0.42 g 0.90 〇Comparative Example 3 14 Synthesis Example 14 10 g 0.42 g 0.42 g 0.51 X 15 Synthesis Example 15 10 g 0.42 g 0.42 g 0.49 X

[Table 5] Curing conditions Temperature 40 ° C -> 110 ° C -> 160 ° C Holding time 10 minutes - 60 minutes - 60 minutes Heating rate - 5. . /min 5 ° C / min - [Table 6-1] Preparation of photosensitive polyimide intermediate composition Table Example Composition No. Poly-proline additive (unit g) Dissolution inhibitor 1 Dissolution inhibitor 2 Flame Retardant Hot Alkali Producer Sensitive Agent 4 16 Synthesis Example 2 - Formula 26 0.262 Formula 29 0.21 - Formula 34 0.47 5 17 Synthesis Example 3 - Formula 26 0.262 Formula 29 0.21 - Formula 34 0.47 6 18 Synthesis Example 4 Formula 25 0.075 Formula 26 0.225 Formula 29 0·3 Formula 32 0.09 Formula 34 0_9 7 19 Synthesis Example 5 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 - Formula 34 0_9 8 20 Synthesis Example 6 - - Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 9 21 Synthesis Example 6 Formula 25 0.075 Formula 26 0.225 殳29 0.3 Formula 32 0.06 Formula 34 0.9 10 22 Synthesis Example 6 - Formula 26 0.375 Formula 29 0_3 Formula 32 0.045 Formula 34 0.68 11 23 Synthesis Example 7 Formula 25 0.075 Formula 26 0.225 Formula 29 0_3 Formula 32 0.09 Formula 34 0.9 12 24 Synthesis Example 7 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.09 Formula 34 0.9 13 25 Synthesis Example 7 Formula 25 0.075 Formula 26 0.225 Formula 30 0.3 Formula 32 0.09 Formula 34 0.9 14 26 Synthesis Example 7 Equation 25 0.075 Equation 26 0.225 ^, 31 0.3 Equation 32 0.09 Formula 34 0.9 15 27 Synthesis Example 7 Formula 25 0.075 Formula 27 0.225 Formula 29 0_3 Formula 32 0.09 Formula 34 0.9 16 28 Synthesis Example 7 Formula 25 0.075 Formula 28 0.225 Formula 29 0.3 Formula 32 0.09 Formula 34 0.9 17 29 Synthesis Example 8 - Formula 27 0.3 Formula 29 0.3 Formula 34 0.75 18 30 Synthesis Example 9 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 19 31 Synthesis Example 10 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 20 32 Synthesis Example 11 Formula 25 0.075 Formula 26 0.225 Fraction 29 0.3 Formula 32 0.06 Formula 34 0.9 21 33 Synthesis Example 12 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 22 34 Synthesis Example 13 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 - 52- 139901.doc 201006867 [Table 6-2 Photosensitive polyamines such as the composition of the composition of the body composition

[Table 7-1] Overview Results of the examples

201006867 As shown in Table 4 of Table 2, the use of the polyimine precursor of the present invention was carried out. J Example 3 showed that the molecular weight (M2/M1) did not decrease. Moreover, the curling strength is also good. It is considered that the result is 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, it is known that the ratio of the other acid dianhydrides to the comparative examples 1 to 3 not only lowers the molecular weight but also lowers 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 exhibited a good residual film ratio. In particular, in Example 8, the dissolution inhibitor was not added and the residual film ratio was 9% by weight. The reason why the general s endures such a result is that the decomposition of the polyimide precursor is inhibited by the development step 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 Applicability] The polyimide precursor of the present invention can be suitably used as a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film of a device having a bump structure, and a multilayer. An interlayer insulating film of a circuit, a top coat of a flexible copper plate, and a liquid crystal alignment film. 139901.doc 54-

Claims (1)

201006867 VII. Patent application scope: A polyimine precursor, which is characterized by comprising an acid dianthine represented by the following general formula (1): [Chemical Formula 1] (1) ❿ (X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms; R1 is a hydrogen atom; an alkyl group having 1 to 7 carbon atoms; an alkoxy group; or a halogen group). 2. The polyimine precursor according to claim 1, wherein the polyimine precursor comprises a diamine represented by the following formula (2): (Y is a divalent organic group having an alkylene group having 2 to 2 carbon atoms; & represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a decyloxy group, or a dentate group). 3. The polyimine precursor according to claim 1 or 2, wherein the polyimine precursor comprises an acid dianhydride represented by the following formula (3): 139901.doc (3) 201006867 3] (a represents an integer of 1 to 20; b represents an integer of 3 to 30; and R3 represents a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 10). 4. The polyimine precursor according to claim 1 or 2, wherein the polyimine precursor comprises a diamine represented by the following formula (4): (4) (Z is a C 2 to 20 alkyl group; I represents a hydrogen atom, a carbon number of 丄 to 10 valence alkyl, alkoxy, or a dentate group; c represents an integer of 2 to 3 〇 ). 5. The polyimine precursor according to claim 2, wherein the above-mentioned polyimine precursor comprises an acid dianhydride represented by the following formula (3): [Chemical 5] 139901.doc (3) 201006867 (a represents an integer from 1 to 15; b represents an integer from 5 to 20; and I represents a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 10). 6. The polyimine precursor according to claim 4, wherein the diamine represented by the above formula (4) is from 25 mol% to 75 mol% in all diamine components. A photosensitive polyimide intermediate composition comprising 1 part by mass of a polyimine precursor according to claim i, 2 or 5, and 5 parts by mass to 35 mass A portion of the sensitizer. 8. The photosensitive polyimide intermediate precursor composition of claim 7, wherein the sensitizer comprises a quinonediazide structure. 9. The photosensitive polyimide intermediate precursor composition of claim 7, which comprises a dissolution inhibitor having a phenolic hydroxyl group. A photosensitive dry film which is obtained by applying a photosensitive polyimide intermediate composition according to claim 7 to a support film, performing 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 1. 12. A polyimine precursor, characterized in that the ratio (Mw2/Mwl) of the weight average molecular weight (Mwl) of the varnish to the weight average molecular weight (Mw2) after desolvation of 12 (rc or less) is 0.7 or more. 1399Dl.doc 201006867 IV. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 139901.doc