JP2006086196A - Wiring board and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin wiring board which has high heat resistance. <P>SOLUTION: The wiring board comprises a base material (10), an insulating layer (13) which is formed on the base material (10) and in which a wiring layer (12) is buried, and a surface protective film (14) which is formed on the insulating layer (13). At least either of the insulating layer (13) and the surface protective film (14) includes a polyimide resin film which is made by hardening a polyimide precursor and contains a filler. The filler is difficult to dissolve in the solution of the polyimide precursor at a temperatures of 50°C or lower, and is one of an insulating inorganic filler and/or resin-coated inorganic filler in which the average diameter of a primary particle is 0.001-1 μm, and an organic filler in which the average diameter of the primary particles is 0.05-100 μm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a wiring board and a manufacturing method of the wiring board.

  In the flexible wiring board, a polyimide cover with a circuit formed on one side, or a copper cover that has a circuit formed on both sides, and a copper plate that has the necessary circuit conduction in the through-holes, with a desired portion opened in advance. An insulating protective film is formed by a method of attaching a lay film with an adhesive, or a method of applying a cover coat with a polyimide cured product in which a polyimide precursor resin composition is applied only to a desired portion and cured by heating (for example, , See Patent Document 1). By laminating the circuit boards thus formed, the circuit boards can be multi-layered.

  When a cover lay film is attached, there are disadvantages such as the presence of the adhesive layer increases the thickness of the substrate and the heat resistance deteriorates due to the adhesive. In addition, since the prior processing such as punching and cutting of the coverlay film is necessary, the processing cost becomes expensive.

When performing a cover coating with a polyimide cured product obtained by applying and curing a polyimide precursor on one side or both sides, a heat treatment of 300 ° C. or higher is required to imidize the polyimide precursor, to prevent oxidation. In addition, heat treatment in an inert gas atmosphere or in a deoxygenated state of a vacuum lower layer is indispensable (see, for example, Patent Document 2). For this reason, there is a disadvantage that the heat treatment time including treatment such as high temperature heating, gas replacement, and deaeration is long. Similarly, when a passivation film is formed by a polyimide cured product obtained by applying and curing this polyimide precursor, a long heat treatment time is required.
Japanese Patent No. 2591599 Japanese Patent No. 2501940

  An object of this invention is to provide the thin wiring board which has high heat resistance, and the method of manufacturing this wiring board easily at low cost.

A wiring board according to an aspect of the present invention includes a base material,
An insulating layer provided on the substrate and embedded with a wiring layer;
A surface protective film provided on the insulating layer;
At least one of the insulating layer and the surface protective film includes a polyimide resin film containing a filler formed by curing a polyimide precursor, and the filler is hardly soluble in a solution of the polyimide precursor at 50 ° C. or less. The primary particle has an average particle diameter of 0.001 to 1 μm, and / or a resin-coated inorganic filler, and the primary particle has an average particle diameter of 0.05 to 100 μm. .

A method for manufacturing a wiring board according to an aspect of the present invention includes:
A step of applying a polyimide precursor composition having a viscosity of 50 to 3000 poise on a substrate by a screen printing method to form a coating film;
The coating film is heated in the temperature range of 60 to 300 ° C. in the air or in an inert gas atmosphere, or heated in the temperature range of 60 to 250 ° C. and then vacuum-heated in the temperature range of 100 to 250 ° C. to obtain a polyimide resin A method of manufacturing a wiring board comprising a step of forming a film,
The polyimide precursor composition is
A polyimide precursor comprising a polyamic acid having a repeating unit represented by the following general formula (1);

(In the general formula (1), Φ may be the same or different and each represents a tetravalent organic group. Ψ may be the same or different, and each represents a divalent organic group. Indicates an integer.)
A thermosetting accelerator blended in a proportion of 3 wt% or more with respect to the polyimide precursor;
Containing a filler compounded in a proportion of 3 wt% or more with respect to the polyimide precursor,
The thermosetting accelerator comprises an organic compound selected from the following (A1) to (A3),
(A1) A substituted or unsubstituted nitrogen-containing heterocyclic compound having an acid dissociation index pKa (logarithm of the reciprocal of the acid dissociation constant Ka) in an aqueous solution in the range of 0 to 8. (A2) Amino acid compound or N-acyl amino acid compound ( A3) Hydroxy compound represented by the following general formula (2)

(In the general formula (2), Ar ₁ and Ar ₂ may be the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group. Z is the same or different. A carboxy group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an acyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxy group, a mercapto group, a substituted or unsubstituted amino group, or a substituted or unsubstituted amino group. X represents an alkyl group, each of which may be the same or different, and is a divalent oxy group, thio group, carbonyl group, carbonylamino group, carbonyloxy group, substituted or unsubstituted amino group, alkyl group, polyfluoroalkyl A represents a group or a single bond, a represents an integer of 0 to 3, b represents an integer of 1 to 5, and c represents an integer of 0 to 5. (The sum of b and c is 2 or more.)
The filler comprises an insulating inorganic filler having an average primary particle diameter of 0.001 to 1 μm and / or an inorganic filler coated with a resin, and an organic filler having an average primary particle diameter of 0.05 to 100 μm. It is characterized by being hardly soluble in a polyimide precursor solution at a temperature of ℃ or lower.

  According to one embodiment of the present invention, a thin wiring board having high heat resistance and a method for easily manufacturing such a wiring board at low cost are provided.

  Embodiments of the present invention will be described below.

  FIG. 1 is a cross-sectional view illustrating a configuration of a wiring board according to an embodiment of the present invention. The illustrated wiring board 10 is a single-sided board flexible circuit board, and an insulating layer 13 is provided on a base insulating base material 11, and a wiring layer 12 made of, for example, copper foil is formed on the insulating layer 13. Further, a surface protective film 14 is provided on these. At least one of the insulating layer 13 and the surface protective film 14 is made of a specific polyimide resin film.

  The wiring board according to the embodiment of the present invention can be a double-sided board flexible wiring board as shown in FIG. In the illustrated wiring board 15, a wiring layer 12 having a laminated structure of a copper foil 16 and a copper plating 17, an insulating layer 13, and a surface protective film 14 are provided on both surfaces of the base insulating base material 11. Also in the case of such a wiring board, at least one of the insulating layer 13 and the surface protective film 14 is made of a specific polyimide resin film, as in the above-described single-sided board flexible wiring board.

  The specific polyimide resin film can be formed by screen printing a polyimide precursor composition. First, the composition used will be described in detail below.

  The polyimide precursor composition contains a polyimide precursor composed of a polyamic acid having a repeating unit represented by the general formula (1).

  Φ in the general formula (1) is a tetravalent organic group, specifically, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group. And a tetravalent group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group directly or directly linked by a bridging group Organic group.

  Examples of the tetravalent organic group introduced as Φ in the general formula (1) include benzene, naphthalene, anthracene, naphthacene, pentacene, hexacene, perylene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, sexiphenyl, and diphenylmethane. , Diphenylethane, diphenylpropane, diphenylbutane, diphenylpentane, diphenyldifluoromethane, diphenyltetrafluoroethane, diphenylhexafluoropropane, diphenyloctafluorobutane, diphenyldecafluoropentane, diphenyl ether, diphenyl sulfide, diphenylsulfone, benzophenone, diphenyldimethylsilane , Diphenyltetramethyldisiloxane, bis (phenylmethyl) benzene, bis (phenylethyl) Benzene, bis (phenylpropyl) benzene, diphenoxybenzene, bis (phenylthio) benzene, bis (phenylsulfonyl) benzene, bis (phenoxyphenyl) methane, bis (phenoxyphenyl) ethane, bis (phenoxyphenyl) propane, bis (phenoxy) Phenyl) difluoromethane, bis (phenoxyphenyl) tetrafluoroethane, bis (phenoxyphenyl) hexafluoropropane, bis (phenoxyphenyl) ether, bis (phenoxyphenyl) sulfide, bis (phenoxyphenyl) sulfone, bis (phenylpropylphenyl) Ether, bis (phenylhexafluoropropylphenyl) ether, bis (phenylpropylphenyl) sulfone, bis (phenylhexafluoropropylphenyl) Phenyl) sulfone, bis (phenoxyphenyl) dimethylsilane, bis (phenoxyphenyl) tetramethyldisiloxane, methane, ethane, propane, butane, pentane, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dialkyl permethyl Polysiloxane, ethylene, cyclopentane, cyclohexane, bicyclohexyl, dicyclohexyl ketone, dicyclohexyl ether, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane, dicyclohexyldifluoromethane, dicyclohexyltetrafluoroethane, dicyclohexylhexafluoropropane, 9-phenyl-9- (tri Fluoromethyl) xanthene, 9,9-bis (trifluoromethyl) Four hydrogen groups from compounds such as xanthene, bicyclo [2,2,2] oct-7-ene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, imidazole, pyrazole, thiazole, oxazole, thiadiazole, oxadiazole An extracted tetravalent organic group is exemplified.

  The tetravalent organic group as described above may be substituted with a characteristic group such as an alkyl group, a halogen group, a polyfluoroalkyl group, a nitro group, or a cyano group. In terms of heat resistance, environmental stability, etc., as Φ, benzene, naphthalene, anthracene, perylene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl ether, Diphenylsulfone, benzophenone, diphenyltetramethyldisiloxane, bis (phenylpropyl) benzene, diphenoxybenzene, diphenoxybiphenyl, bis (phenoxyphenyl) propane, bis (phenoxyphenyl) hexafluoropropane, bis (phenoxyphenyl) ether and bis A tetravalent organic group obtained by extracting four hydrogen groups from a compound such as (phenoxyphenyl) sulfone is particularly preferable.

  Ψ in the general formula (1) is a divalent organic group, specifically, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group. And a divalent group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group directly or directly linked to each other by a bridging group Organic group.

  Examples of the divalent organic group introduced as Ψ in the general formula (1) include benzene, naphthalene, anthracene, naphthacene, pentacene, hexacene, perylene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, sexiphenyl, and diphenylmethane. , Diphenylethane, diphenylpropane, diphenylbutane, diphenylpentane, diphenyldifluoromethane, diphenyltetrafluoroethane, diphenylhexafluoropropane, diphenyloctafluorobutane, diphenyldecafluoropentane, diphenyl ether, diphenyl sulfide, diphenylsulfone, benzophenone, diphenyldimethylsilane , Diphenyltetramethyldisiloxane, bis (phenylmethyl) benzene, bis (phenylethyl) Benzene, bis (phenylpropyl) benzene, diphenoxybenzene, bis (phenylthio) benzene, bis (phenylsulfonyl) benzene, diphenoxybiphenyl, bis (phenoxyphenyl) methane, bis (phenoxyphenyl) ethane, bis (phenoxyphenyl) propane , Bis (phenoxyphenyl) difluoromethane, bis (phenoxyphenyl) tetrafluoroethane, bis (phenoxyphenyl) hexafluoropropane, bis (phenoxyphenyl) ether, bis (phenoxyphenyl) sulfide, bis (phenoxyphenyl) sulfone, bis ( Phenylpropylphenyl) ether, bis (phenylhexafluoropropylphenyl) ether, bis (phenylpropylphenyl) sulfone, bis (phenyl) Hexafluoropropylphenyl) sulfone, bis (phenoxyphenyl) dimethylsilane, bis (phenoxyphenyl) tetramethyldisiloxane, methane, ethane, propane, butane, pentane, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, Dialkyl permethyl polysiloxane, ethylene, cyclopentane, cyclohexane, bicyclohexyl, dicyclohexyl ketone, dicyclohexyl ether, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane, dicyclohexyldifluoromethane, dicyclohexyltetrafluoroethane, dicyclohexylhexafluoropropane, 9-phenyl-9 -(Trifluoromethyl) xanthene, 9,9- Su (trifluoromethyl) xanthene, bicyclo [2,2,2] oct-7-ene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, imidazole, pyrazole, thiazole, oxazole, oxadiazole, thiadiazole, etc. Examples thereof include divalent organic groups obtained by extracting two hydrogen groups from the above.

  The divalent organic group as described above may be substituted with a characteristic group such as an alkyl group, a halogen group, a polyfluoroalkyl group, a nitro group, or a cyano group. In terms of heat resistance, environmental stability, etc., Ψ includes benzene, naphthalene, anthracene, perylene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenyl ether, Diphenylsulfone, benzophenone, diphenyltetramethyldisiloxane, bis (phenylpropyl) benzene, diphenoxybenzene, diphenoxybiphenyl, bis (phenoxyphenyl) propane, bis (phenoxyphenyl) hexafluoropropane, bis (phenoxyphenyl) ether and bis A divalent organic group obtained by extracting two hydrogen groups from a compound such as (phenoxyphenyl) sulfone is particularly preferable.

The polyimide precursor (polyamide acid) represented by the general formula (1) includes, for example, a tetracarboxylic dianhydride component represented by the following general formula (3) and a diamine compound component represented by the following general formula (4). Can be synthesized in an organic solvent.

(In the above general formula (3), φ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group, and aliphatic And a tetravalent organic group selected from the group consisting of compound groups in which an aromatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group are connected to each other directly or by a bridging group.

(In the above general formula (4), Ψ is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group, and aliphatic And a divalent organic group selected from the group consisting of compound groups in which an aromatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group are directly or mutually linked by a bridging group.)
Φ in the general formula (3) is a tetravalent organic group, specifically an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group. And a tetravalent group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group directly or directly linked by a bridging group Organic group.

  Examples of the tetravalent organic group introduced as Φ in the general formula (3) include a tetravalent organic group shown as Φ in the general formula (1), and Ψ in the general formula (4). Examples of the divalent organic group to be introduced include a divalent organic group represented as ψ in the general formula (1).

  Examples of the tetracarboxylic dianhydride represented by the general formula (3) include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3- (Trifluoromethyl) pyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ′, 4 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -terphenyltetracarboxylic dianhydride, 3,3 "', 4,4"'-quaterphenyltetracarboxylic dianhydride, 3,3 "", 4,4 ""- Kink phenyl tetracarboxylic acid Water, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, methylene-4,4′-diphthalic dianhydride, 1,1-ethylidene-4,4′-diphthalic dianhydride 2,2-propylidene-4,4′-diphthalic dianhydride, 1,2-ethylene-4,4′-diphthalic dianhydride, 1,3-trimethylene-4,4′-diphthalic dianhydride 1,4-tetramethylene-4,4′-diphthalic dianhydride, 1,5-pentamethylene-4,4′-diphthalic dianhydride, 1,1,1,3,3,3- Hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride, difluoromethylene-4,4′-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene -4,4'-diphthalic dianhydride, 1,1,2,2,3,3-hexaph Fluoro-1,3-trimethylene-4,4′-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4′- Diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4′-diphthalic dianhydride, oxy-4 , 4′-diphthalic dianhydride, thio-4,4′-diphthalic dianhydride, sulfonyl-4,4′-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene Dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4- Bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3 4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4- Dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis 4- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1 , 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6 7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetra Methyldisiloxa Dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic acid Dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyl Tetracarboxylic dianhydride, carbonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride 1,2-ethylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4′-bis (cyclohexane-1,2-dicarbohydrate) Acid) dianhydride, 2,2-propylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2 -Propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4 '-Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2'-difluoro-3,3' , 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-difluoro-3,3 ′ , 4,4'-biphenyltetracarbo Acid dianhydride, 2,2 ′, 5,5 ′, 6,6′-hexafluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis (trifluoro Methyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 6,6′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 5,5′-tetrakis (trifluoromethyl) -3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 5,5 ′, 6,6′-tetrakis (trifluoromethyl ) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5 ', 6,6'-hexakis (trifluoromethyl) -3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, oxy-4,4'-bis (3-fluorophthalic acid) dianhydride, oxy-4,4'-bis (5-fluorophthalic acid) dianhydride, oxy- 4,4′-bis (6-fluorophthalic acid) dianhydride, oxy-4,4′-bis (3,5,6-trifluorophthalic acid) dianhydride, oxy-4,4′-bis [ 3- (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4′-bis [5- (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4′-bis [6- (tri Fluoromethyl) phthalic acid] dianhydride, oxy-4,4′-bis [3,5-bis (to Fluoromethyl) phthalic acid] dianhydride, oxy-4,4′-bis [3,6-bis (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4′-bis [5,6-bis (Trifluoromethyl) phthalic acid] dianhydride, oxy-4,4′-bis [3,5,6-tris (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4′-bis (3 -Fluorophthalic acid) dianhydride, sulfonyl-4,4'-bis (5-fluorophthalic acid) dianhydride, sulfonyl-4,4'-bis (6-fluorophthalic acid) dianhydride, sulfonyl-4 , 4′-bis (3,5,6-trifluorophthalic acid) dianhydride, sulfonyl-4,4′-bis [3- (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4 ′ -Bis [5- (trifluoromethyl) phthalic acid Dianhydride, sulfonyl-4,4'-bis [6- (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4'-bis [3,5-bis (trifluoromethyl) phthalic acid] Anhydride, sulfonyl-4,4′-bis [3,6-bis (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4′-bis [5,6-bis (trifluoromethyl) phthalic acid Dianhydride, sulfonyl-4,4′-bis [3,5,6-tris (trifluoromethyl) phthalic acid] dianhydride, 1,1,1,3,3,3-hexafluoro-2, 2-propylidene-4,4′-bis (3-fluorophthalic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis (5 -Fluorophthalic acid) dianhydride, 1,1,1,3,3,3-hex Safluoro-2,2-propylidene-4,4′-bis (6-fluorophthalic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4 ′ -Bis (3,5,6-trifluorophthalic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis [3- (tri Fluoromethyl) phthalic acid] dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis [5- (trifluoromethyl) phthalic acid] dianhydride 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis [6- (trifluoromethyl) phthalic acid] dianhydride, 1,1,1, 3,3,3-Hexafluoro-2,2-propylidene-4,4'-bis [3,5-bis Trifluoromethyl) phthalic acid] dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis [3,6-bis (trifluoromethyl) phthale Acid] dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis [5,6-bis (trifluoromethyl) phthalic acid] dianhydride 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis [3,5,6-tris (trifluoromethyl) phthalic acid] dianhydride, 9- Phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic acid Anhydride and bicyclo [2,2,2] oct-7-e Such as 2,3,5,6-tetracarboxylic acid dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  Tetracarboxylic dianhydride is preferably used in a proportion of 0.8 molar equivalents or more, more preferably 0.9 molar equivalents or more, of all acid anhydride components. When there are too few compounding quantities of tetracarboxylic dianhydride, there exists a possibility that the heat resistance of the polyimide resin obtained may fall.

  Examples of the diamine compound represented by the general formula (4) include 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3′-diaminobiphenyl, and 3,4′-. Diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3 "-diaminoterphenyl, 4,4" -diaminoterphenyl, 3,3 "'-diaminoquaterphenyl, 4,4"'-diaminoquaterphenyl Oxy-3,3′-dianiline, oxy-4,4′-dianiline, thio-3,3′-dianiline, thio-4,4′-dianiline, sulfonyl-3,3′-dianiline, sulfonyl-4, 4′-dianiline, methylene-3,3′-dianiline, methylene-4,4′-dianiline, 1,2-ethylene-3,3′-dianiline, 1,2-ethane Tylene-4,4′-dianiline, 2,2-propylidene-3,3′-dianiline, 2,2-propylidene-4,4′-dianiline, 1,1,1,3,3,3-hexafluoro- 2,2-propylidene-3,3′-dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-dianiline, 1,1,2,2,3 , 3-hexafluoro-1,3-propylene-3,3′-dianiline, 1,1,2,2,3,3-hexafluoro-1,3-propylene-4,4′-dianiline, 1,3 -Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenylthio) benzene, 1,3-bis (4-aminophenylthio) benzene 1,3-bis (3-aminophen Rusulfonyl) benzene, 1,3-bis (4-aminophenylsulfonyl) benzene, 1,3-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4 -Aminophenyl) -2-propyl] benzene, 1,3-bis [2- (3-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,3 -Bis [2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenylthio) benzene, 1,4-bis (4-aminophenylthio) benzene, 1,4-bis (3-aminophenylsulfonyl) benzene , , 4-bis (4-aminophenylsulfonyl) benzene, 1,4-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminophenyl) -2 -Propyl] benzene, 1,4-bis [2- (3-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,4-bis [2- ( 4-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1, 3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 5-fluoro-1,3 -Phenylenediamine, 2-fluoro-1,4-fluoro Enylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2,4,5,6-hexafluoro-1,3-phenylenediamine, 2,3,5,6-hexafluoro-1,4-phenylenediamine 3,3′-diamino-5,5′-difluorobiphenyl, 4,4′-diamino-2,2′-difluorobiphenyl, 4,4′-diamino-3,3′-difluorobiphenyl, 3,3 ′ -Diamino-2,2 ', 4,4', 5,5 ', 6,6'-octafluorobiphenyl, 4,4'-diamino-2,2', 3,3 ', 5,5', 6 , 6′-octafluorobiphenyl, oxy-5,5′-bis (3-fluoroaniline), oxy-4,4′-bis (2-fluoroaniline), oxy-4,4′-bis (3-fluoro Aniline), sulfoni -5,5'-bis (3-fluoroaniline), sulfonyl-4,4'-bis (2-fluoroaniline), sulfonyl-4,4'-bis (3-fluoroaniline), 1,3-bis ( 3-aminophenoxy) -5-fluorobenzene, 1,3-bis (3-amino-5-fluorophenoxy) benzene, 1,3-bis (3-amino-5-fluorophenoxy) -5-fluorobenzene, 5 -(Trifluoromethyl) -1,3-phenylenediamine, 2- (trifluoromethyl) -1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 2,2 '-Bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, oxy-5 '-Bis [3- (trifluoromethyl) aniline], oxy-4,4'-bis [2- (trifluoromethyl) aniline], oxy-4,4'-bis [3- (trifluoromethyl) aniline ], Sulfonyl-5,5′-bis [3- (trifluoromethyl) aniline], sulfonyl-4,4′-bis [2- (trifluoromethyl) aniline], sulfonyl-4,4′-bis [3 -(Trifluoromethyl) aniline], 1,3-bis (3-aminophenoxy) -5- (trifluoromethyl) benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] benzene 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] -5- (trifluoromethyl) benzene, 3,3′-bis (trifluoromethyl) -5,5 ′ -Diaminobiphenyl, bis (3-aminophenoxy) dimethylsilane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (3-aminophenyl) -1,1,3,3-tetramethyldisiloxane, , 3-bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane, methylenediamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1, 5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,2-bis (3-aminopropoxy) Ethane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (3-aminocyclohexyl) methane, bis ( -Aminocyclohexyl) methane, 1,2-bis (3-aminocyclohexyl) ethane, 1,2-bis (4-aminocyclohexyl) ethane, 2,2-bis (3-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-aminocyclohexyl) ether, bis (4-aminocyclohexyl) ether, bis (3-aminocyclohexyl) sulfone, bis (4-aminocyclohexyl) sulfone, 2,2-bis ( 3-aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 1,3-xylylenediamine, 1,4-xylylenediamine, 1,8-diaminonaphthalene, 2, -Diaminonaphthalene, 2,6-diaminonaphthalene, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyrazine, 2,4-diamino-s-triazine, 1,3-bis (aminomethyl) ) Cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-bis (3-aminopropyldimethylsilyl) benzene and 1,3-bis (3-aminopropyl) -1,1,3,3-tetra Examples thereof include phenyldisiloxane. These diamine compounds may be used alone or in combination of two or more.

  The diamine compound is preferably used in a proportion of 0.8 molar equivalents or more, more preferably 0.9 molar equivalents or more, of all the amine compound components. When there are too few compounding quantities of a diamine compound, there exists a possibility that the heat resistance of the polyimide resin obtained may fall.

A diamine compound represented by the following general formula (5), that is, a bis (aminoalkyl) peralkylpolysiloxane compound may be used in combination with these diamine compounds.

(In the general formula (5), Rs may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, q and r are integers of 1 to 10, and p is a positive integer. .)
Examples of the bis (aminoalkyl) perfluoropolysiloxane compound represented by the general formula (5) include 1,3-bis (aminomethyl) -1,1,3,3-tetramethyldisiloxane, 1,3 -Bis (2-aminoethyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3 -Bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (5-aminopentyl) -1,1,3,3-tetramethyldisiloxane, 1,3 -Bis (6-aminohexyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (7-aminoheptyl) -1,1,3,3-tetramethyldisiloxane, 1,3 -Bis (8-aminooctyl ) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (10-aminodecyl) -1,1,3,3-tetramethyldisiloxane, 1,5-bis (3-aminopropyl) -1,1,3,3,5,5-hexamethyltrisiloxane, 1,7-bis (3-aminopropyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane 1,11-bis (3-aminopropyl) -1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane, 1,15-bis (3- Aminopropyl) -1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane, 1,19-bis (3- Aminopropyl) -1,1,3,3,5,5,7,7,9,9,11,1 , And the like 13,13,15,15,17,17,19,19- eicosapentaenoic methyl deca-siloxane.

  The bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (5) has an effect of improving adhesion and adhesion of a polyimide resin to a semiconductor substrate such as a glass substrate or a silicon substrate. These compounds are preferably used in a mixture of 0.02 to 0.1 molar equivalent among all diamine components. When the compound represented by the general formula (5) is excessively blended, the heat resistance of the polyimide resin may be lowered.

  Furthermore, in order to control the degree of polymerization of the polyamic acid, a dicarboxylic acid anhydride or a monoamine compound can be used as a terminal treating agent. Examples of dicarboxylic acid anhydrides that can be used include maleic anhydride, citraconic anhydride, dimethylmaleic anhydride, ethylmaleic anhydride, diethylmaleic anhydride, propylmaleic anhydride, and butylmaleic anhydride. , Chloromaleic anhydride, dichloromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride, fluoromaleic anhydride, difluoromaleic anhydride, (trifluoromethyl) maleic anhydride, bis ( Trifluoromethyl) maleic anhydride, cyclobutanedicarboxylic anhydride, cyclopentanedicarboxylic anhydride, cyclohexanedicarboxylic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylendome Rentetrahydrophthalic anhydride, phthalic anhydride, methylphthalic anhydride, ethylphthalic anhydride, dimethylphthalic anhydride, fluorophthalic anhydride, difluorophthalic anhydride, chlorophthalic anhydride, dichlorophthalic anhydride , Bromophthalic anhydride, dibromophthalic anhydride, nitrophthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 3-phenoxyphthalic anhydride, 4-phenoxyphthalic acid Anhydride, 3- (phenylsulfonyl) phthalic anhydride, 4- (phenylsulfonyl) anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 1,2-naphthalenedicarboxylic acid Anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphth Range carboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid anhydride, 2,3-pyridinedicarboxylic acid anhydride, 3,4- Examples of monoamine compounds that can be used include pyridinedicarboxylic acid anhydride, and examples include methylamine, ethylamine, protylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, and 1- (3-aminopropyl). -1,1,3,3,3-pentamethyldisiloxane, vinylamine, allylamine, glycine, alanine, aminobutyric acid, valine, norvaline, isovaline, leucine, norleucine, isoleucine, glutamine, glutamic acid, tryptophan, aminocrotonic acid , Aminoacetonitrile, aminopropionitrile, aminocrotononitrile, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, aminoadamantane, aminobenzocyclobutane, aminocaprolactam, aniline, chloroaniline, Dichloroaniline, bromoaniline, dibromoaniline, fluoroaniline, difluoroaniline, nitroaniline, dinitroaniline, toluidine, xylidine, ethylaniline, anisidine, phenetidine, aminoacetanilide, aminoacetophenone, aminobenzoic acid, aminobenzaldehyde, aminobenzonitrile, amino Phthalonitrile, aminobenzotrifluoride, aminostyrene, aminos Ruben, aminoazobenzene, aminodiphenyl ether, aminodiphenylsulfone, aminobenzamide, aminobenzenesulfonamide, aminophenylmaleimide, aminophenylphthalimide, aminobiphenyl, aminoterphenyl, aminonaphthalene, aminoacridine, aminoanthraquinone, aminofluorene, aminofluorenone, Aminopyrrolidine, Aminopiperazine, Aminopiperidine, Aminohomopiperidine, Aminomorpholine, Aminobenzodioxole, Aminobenzodioxan, Aminopyridine, Aminopyridazine, Aminopyrimidine, Aminopyrazine, Aminoquinoline, Aminocinnoline, Aminophthalazine, Amino Quinazoline, aminoquinoxaline, aminopyrrole, aminoimidazole, aminopyrrole Sol, aminotriazole, aminooxazole, aminoisoxazole, aminothiazole, aminoisothiazole, aminoindole, aminobenzimidazole, aminoindazole, aminobenzoxazole, aminobenzothiazole, benzylamine, phenethylamine, phenylpropyriamine, phenylbutylamine, benz Examples include hydrylamine, aminoethyl-1,3-dioxolane, aminoethylpyrrolidine, aminoethylpiperazine, aminoethylpiperidine, aminoethylmorpholine, aminopropylimidazole and aminopropylcyclohexane.

  The blending amount of the dicarboxylic acid anhydride and the monoamine compound as described above can be appropriately selected according to the use, viscosity, etc. For example, 0.02 to 0 with respect to the tetracarboxylic dianhydride or diamine compound. About 4 molar equivalents are preferred.

  A method for synthesizing the polyamic acid represented by the general formula (1) is not particularly limited, but a method of polymerizing under an inert gas atmosphere and under an anhydrous condition in an organic polar solvent is preferable. Examples of the organic polar solvent used in this reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, N -Acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethyl phosphortriamide, N-methyl-ε-caprolactam, N-acetyl-ε-caprolactam, 1 , 2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- ( 2-methoxyethoxy) ethyl] ether, 1-acetoxy-2-methoxyethane, 1-acetoxy Ci-2-ethoxyethane, (2-acetoxyethyl) (2-methoxyethyl) ether, (2-acetoxyethyl) (2-ethoxyethyl) ether, methyl 3-methoxypropionate, tetrahydrofuran, 1,3-dioxane, Examples include 1,3-dioxolane, 1,4-dioxane, pyrroline, pyridine, picoline, dimethyl sulfoxide, sulfolane, γ-butyrolactone, propylene carbonate, phenol, cresol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and acetonyl acetone. These organic solvents may be used alone or in combination of two or more. The reaction temperature is generally −20 to 100 ° C., preferably −5 to 30 ° C. The reaction pressure is not particularly limited, and can be sufficiently carried out at normal pressure. The reaction time varies depending on the type of tetracarboxylic dianhydride and the type of reaction solvent, and usually 1 to 24 hours is sufficient.

  The polyamic acid thus obtained preferably has an inherent viscosity of a 0.5 wt% -N-methyl-2-pyrrolidone solution of 0.3 (dL / g) or more. The reason for this is that if the inherent viscosity of the polyamic acid is too low, that is, if the degree of polymerization of the polyamic acid is too low, it may not be possible to obtain a sufficiently heat-resistant polyimide resin.

  Examples of the polyimide precursor (polyamic acid) represented by the general formula (1) include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4, 4′-biphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -terphenyltetracarboxylic dianhydride, methylene-4,4′-diphthalic dianhydride, 1,1-ethylidene-4 , 4′-diphthalic dianhydride, 2,2-propylidene-4,4′-diphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4, 4'-diphthalic dianhydride, oxy-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride 1,4,5,8-naphthalenetetraca Boronic acid dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride and 9,9-bis (trifluoromethyl) xanthene-2,3 Tetracarboxylic dianhydrides such as 6,7-tetracarboxylic dianhydride, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3 ″ -diaminoterphenyl, 4,4 ″ -diaminoterphenyl, oxy-3,3′-dianiline, oxy-3,4′-dianiline, oxy-4,4 ′ -Dianiline, sulfonyl-3,3'-dianiline, sulfonyl-4,4'-dianiline, methylene-3,3'-dianiline, methylene-4,4'-dianiline 2,2-propylidene-3,3'-dianiline, 2,2-propylidene-4,4'-dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-3,3 '-Dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-dianiline, 1,1,1,3,3,3-hexafluoro-2,2 -Propylidene-5,5'-di (2-toluidine), 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis (2-aminophenol), 1 , 3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,3- Bis [2- (4-aminophenyl) -2-propyl] Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis [2- (3-aminophenyl) -2-propyl] benzene, 1 , 4-bis [2- (4-aminophenyl) -2-propyl] benzene, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [ 4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) Phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propyl Pan, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropane, 5- (trifluoromethyl) -1,3-phenylenediamine, 2,2′-bis (trifluoromethyl) -4,4′- Diaminobiphenyl, 3,3′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, oxy-5,5′-bis [3- (trifluoromethyl) aniline], 1,8-diaminonaphthalene, 2 , 7-diaminonaphthalene, 2,6-diaminonaphthalene, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and other diamine compounds are reacted in an organic solvent. Polyamic acid synthesized in this manner is desirable, among which pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride, oxy-4,4′-diphthalic dianhydride, 9 -Phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride and 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic acid Tetracarboxylic dianhydrides such as dianhydrides, 1,3-phenylenediamine, 1,4-phenylenediamine, oxy-3,3′-dianiline, oxy-3,4′-dianiline, oxy-4,4 '-Dianiline, sulfonyl-3,3'-dianiline, sulfonyl-4,4'-dianiline, methylene-3,3'-dianiline, methylene-4,4'-dianiline, 2,2-propylidene-3,3' -Dianiline, 2,2-propylidene-4,4'-dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-3,3'-dianiline, 1,1,1, 3,3,3-hexafluoro-2,2-propylidene-4,4′-dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-5,5′-di ( 2-toluidine), 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis (2-aminophenol), 1,3-bis (3-aminophenoxy) Benzene, 1,3-bis (4-a Nophenoxy) benzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) Benzene, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, oxy-5,5′- Synthesized by reacting diamine compounds such as bis [3- (trifluoromethyl) aniline], 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane in an organic solvent. Polyamic acid is preferred.

  In order to cure the polyimide precursor as described above, any one of (A1), (A2), and (A3) thermosetting accelerator is blended in the polyimide precursor composition. The thermosetting accelerator that can be used is described in detail below. (A1) A thermosetting accelerator comprising a substituted or unsubstituted nitrogen-containing heterocyclic compound having an acid dissociation index pKa (logarithm of the reciprocal of acid dissociation constant Ka) in an aqueous solution in the range of 0 to 8 includes, for example, imidazole , Pyrazole, triazole, tetrazole, benzimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline, dipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, feline Nanthridine, benzoquinoline, phenanthroline, phenazine, triazine, tetrazine, pteridine, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothi Tetrazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, triethylenediamine, a compound having an unsubstituted nitrogen-containing heterocyclic groups such as hexamethylene tetramine and the like. These heterocyclic groups may be substituted with various characteristic groups shown below to constitute a substituted nitrogen-containing heterocyclic group.

  Examples of the characteristic group introduced into the nitrogen-containing heterocyclic group include a di-substituted amino group (dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group). , Diphenethylamino group, diphenylamino group, ditolylamino group, dixylamino group, methylphenylamino group, benzylmethylamino group, etc., mono-substituted amino group (methylamino group, ethylamino group, propylamino group, isopropylamino group) Tert.-butylamino group, anilino group, anisino group, phenidino group, toluidino group, xylidino group, pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group, etc., cyclic amino group (pyrrolidino group, piperidino group, piperazino group) Group, morpho Group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, 1-triazolyl group, etc.), acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonylamino group, Trifluoroacetylamino group, etc.), sulfonylamino group (mesylamino group, ethylsulfonylamino group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group, methyl Sulfamoylamino group, sulfanylamino group, acetylsulfanylamino group, etc.), amino group, hydroxyamino group, ureido group, semicarbazide group, carbazide group, disubstituted hydrazino group (dimethylhydrazino group, di Phenylhydrazino group, methylphenylhydrazino group, etc.), mono-substituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino group, amidino group, hydroxy group, oxime group ( Hydroxyiminomethyl group, methoxyiminomethyl group, ethoxyiminomethyl group, hydroxyiminoethyl group, hydroxyiminopropyl group, etc.), alkoxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.), cyano group, cyanato group , Thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazolyloxy group, acetoxy Group), thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.), mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and salts thereof, oxy Carbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allophanoyl group, oxamoyl group, Succinamoyl group, etc.), thiocarboxyl group and its salt, dithiocarboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.) ), Acyl groups (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group, trifluoroacetyl group, etc.), thioacyl group (thioformyl group, thioacetyl group, thiobenzoyl group) , Pyridinethiocarbonyl group, etc.), sulfinic acid group and its salt, sulfonic acid group and its salt, sulfinyl group (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group etc.), sulfonyl group (mesyl group, ethylsulfonyl group, phenyl) Sulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, acetylsulfanylyl group), oxysulfoni Groups (methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl groups (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl) Group, pyridylthiosulfonyl group, etc.), aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group, acetaminophenylsulfuric group) Famoyl group, pyridylsulfamoyl group, etc.), ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylphenylammonio group, pyridinio group, quinolinio group, etc.) , Azo group (phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoxy group, alkyl halide group (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trifluoromethyl group) , Pentafluoroethyl group, heptafluoropropyl group, etc.), hydrocarbon group (alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, organosilicon group (silyl group, disilanyl group, trimethylsilyl group, triphenyl) Examples of the substituent to be introduced include a hydroxy group, an oxy group, an oxime group, an aminocarbonyl group, an alkoxyalkyl group, a disubstituted amino group, a monosubstituted amino group, a cyclic amino group, Acylamino group, amino group, ureido group, mel Script group, thio group is particularly desirable.

  (A2) Examples of thermosetting accelerators comprising amino acid compounds or N-acyl amino acid compounds include glycine, sarcosine, dimethylglycine, betaine, alanine, β-alanine, α-aminobutyric acid, β-aminobutyric acid, and γ-amino. Butyric acid, γ-amino-β-oxobutyric acid, valine, β-aminoisovaleric acid, γ-aminoisovaleric acid, norvaline, β-aminovaleric acid, γ-aminovaleric acid, δ-aminovaleric acid, leucine, isoleucine, norleucine , Serine, α-methylserine, isoserine, α-methylisoserine, cycloserine, threonine, o-methylthreonine, allothreonine, o-methylallothreonine, roseonin, trans-3-aminocyclohexanecarboxylic acid, cis-3-aminocyclohexane Carboxylic acid, ε-amine caproic acid, ω-amino Dodecanoic acid, β-hydroxyvaline, β-hydroxyisoleucine, α-hydroxy-β-aminoisovaleric acid, ε-diazo-δ-oxonorleucine, α-amino-ε-hydroxyaminocaproic acid, cysteine, cystine, S-methyl Cysteine, S-methylcysteine sulfoxide, cysteic acid, homocysteine, homocystin, methionine, penicillamine, taurine, α, β-diaminopropionic acid, ornithine, lysine, arginine, canalin, canavanine, δ-hydroxylysine, aspartic acid, asparagine, Isoasparagine, glutamic acid, glutamine, isoglutamine, α-methylglutamic acid, β-hydroxyglutamic acid, γ-hydroxyglutamic acid, α-aminoadipic acid, citrulline, cystathionine, phenyla Nin, α-methylphenylalanine, o-chlorophenylalanine, m-chlorophenylalanine, p-chlorophenylalanine, o-fluorophenylalanine, m-fluorophenylalanine, p-fluorophenylalanine, β- (2-pyridyl) alanine, tyrosine, dichlorotyrosine , Dibromothiocin, diiodotyrosine, 3,4-dihydroxyphenylalanine, α-methyl-3,4-dihydroxyphenylalanine, phenylglycine, anilinoacetic acid, 2-pyridylglycine, tryptophan, histidine, 1-methylhistidine, 2-thiol Examples include amino acid compounds such as histidine, proline, and hydroxyproline. The amino group in these amino acid compounds may be substituted with the following substituents to constitute N-acyl amino acid compounds.

  In this case, examples of the substituent that can be introduced include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, acryloyl group Group, propioroyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cyclopentanecarbonyl group, cyclohexanecarbonyl group, benzoyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group , Thenoyl group, picolinoyl group, nicotinoyl group, isonicotinoyl group, quinolinecarbonyl group, pyridazinecarbonyl group, pyrimidinecarbonyl group, pyrazinecarbonyl group, imidazolecarbonyl group, Nzoimidazolecarbonyl group, thiazolecarbonyl group, benzothiazolecarbonyl group, oxazolecarbonyl group, benzoxazolecarbonyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azelaoil group, sebacoyl group , Maleoyl group, fumaroyl group, citraconoyl group, mesaconoyl group, mesoxalyl group, oxalacetyl group, camphoroyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, oxaloyl group, ethoxalyl group, glyoxyloyl group, pyrvoyl group, Acetoacetyl group, Mesoxalo group, Oxalaceto group, Cysteinyl group, Homocysteinyl group, Tryptophyll group, Alanyl group, β-alanyl group, Arginyl group, Cystathio Nyl group, cystyl group, glycyl group, histidyl group, homoceryl group, isoleucyl group, lanthionyl group, leucyl group, lysyl group, methionyl group, norleusyl group, norvalyl group, ornithyl group, prolyl group, sarcosyl group, seryl group, threonyl group , Acyl groups such as a tyronyl group, a tyrosyl group, and a valyl group.

  (A3) Examples of the thermosetting accelerator comprising the hydroxy compound represented by the general formula (2) include benzene, naphthalene, anthracene, phenanthrene, tetralin, azulene, biphenylene, acenaphthylene, acenaphthene, fluorene, triphenylene, pyrene, and chrysene. , Picene, perylene, benzopyrene, rubicene, coronene, ovalene, indene, pentalene, heptalene, indacene, phenalene, fluoranthene, acephenanthrylene, acanthrylene, naphthacene, pleiaden, pentaphen, pentacene, tetraphenylene, hexaphene, hexacene, Fragrances such as trinaphthylene, heptaphene, heptacene, pyranthrene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, sexiphenyl A hydrocarbon group is a carboxy group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an acyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxy group, a mercapto group, a substituted or unsubstituted amino group, or a substituted or unsubstituted group. Examples thereof include substituted aromatic hydrocarbon groups substituted with at least two kinds of characteristic groups among aminoalkyl groups.

  The above-mentioned thermosetting accelerators are all low temperature curing accelerators that accelerate the curing of polyamic acid at about 200 ° C. or less. These low temperature curing accelerators may be used alone or in combination of two or more.

  In terms of low vaporization point (boiling point, sublimation point, decomposition point), curing acceleration effect and solubility in polyamic acid solution, thermosetting accelerators include imidazole, 1,2,4-triazole, benzimidazole. , Purine, quinoline, isoquinoline, pyridazine, phthalazine, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, phenanthroline, phenazine, 2,2'-dipyridyl, 2,4'-dipyridyl, 4,4'-dipyridyl 2,2′-diquinolyl, 1-methylimidazole, 1-ethylimidazole, 1-methylbenzimidazole, 1-ethylbenzimidazole, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 8-hydroxyquinoline, Picolinic acid amide, nicotine Amide, isonicotinic acid amide, hydroxynicotinic acid, picolinic acid ester, nicotinic acid ester, isonicotinic acid ester, 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, picolinaldehyde, nicotinaldehyde, isonicotined aldehyde, 3 Nitropyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2- (hydroxymethyl) pyridine, 3- (hydroxymethyl) pyridine, 4- (hydroxymethyl) pyridine, 2- (hydroxyethyl) pyridine 3- (hydroxyethyl) pyridine, 4- (hydroxyethyl) pyridine, picoline aldoxime, nicotine aldoxime, isonicotine aldoxime, hydantoin, histidine, uracil, barbituric acid, diallic acid, cytosine Anilinoacetic acid, 2-pyridylglycine, tryptophan, proline, N-acetylglycine, hippuric acid, N-picolinoylglycine, N-nicotinoylglycine, N-isonicotinoylglycine, N-acetylalanine, N-benzoylalanine, N-picolinoylalanine, N-nicotinoylalanine, N-isonicotinoylalanine, α- (acetylamino) butyric acid, α- (benzoylamino) butyric acid, α- (picolinoylamino) butyric acid, α- (nicotinoylamino) ) Butyric acid, α- (isonicotinoylamino) butyric acid, N-acetylvaline, N-benzoylvaline, N-picolinoylvaline, N-nicotinoylvaline, N-isonicotinoylvaline, 2-hydroxybenzoic acid, 3- Hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,4-dihydro Cibenzoic acid, 2- (hydroxyphenyl) acetic acid, 3- (hydroxyphenyl) acetic acid, 4-hydroxyphenylacetic acid, 3- (4-hydroxyphenyl) propionic acid, 2- (4-hydroxyphenyl) isovaleric acid, 2- Phenolsulfonic acid, 3-phenolsulfonic acid, 4-phenolsulfonic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2 -Hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde and the like are particularly preferred.

  These thermosetting accelerators are blended in a proportion of 3 wt% or more with respect to the polyimide precursor. If the ratio of the thermosetting accelerator is less than 3 wt%, the imidation of the polyamic acid becomes insufficient because of too little, and a good polyimide resin cannot be obtained. The blending amount of the thermosetting accelerator is preferably 100 wt% of the polyamide precursor at the maximum. If the amount of the thermosetting accelerator is too large, the storage stability of the polyimide precursor composition may decrease, or the amount of the thermosetting accelerator remaining after heat curing may increase and adversely affect various properties. There is. The blending amount of the thermosetting accelerator is preferably 5 to 50 wt% with respect to the polyimide precursor.

A specific filler must be mix | blended with the polyimide precursor composition used in embodiment of this invention.
The filler is required to be hardly soluble in the polyimide precursor solution at 50 ° C. or lower. Slightly soluble means that the solubility of the filler in the polyimide precursor solution is 0.1% or less. More preferably, it is insoluble, that is, the solubility of the filler in the polyimide precursor solution is 0.01% or less.

  Further, the filler may be composed of an insulating inorganic filler having an average primary particle diameter of 0.001 to 1 μm and / or an inorganic filler coated with a resin, or an organic filler having an average primary particle diameter of 0.05 to 100 μm. is necessary. A primary particle refers to a unit particle that is considered to be single crystallographically. The average diameter can be visually measured from an image photograph obtained by, for example, a scanning electron microscope (SEM). Alternatively, mechanical measurement may be performed by particle size distribution measurement using a dynamic light scattering method, a static light scattering method, or the like.

  Examples of the insulating inorganic filler include alumina, silica, titanium oxide, zinc oxide, zirconium oxide, aluminum nitride, talc, quartz powder, calcium carbonate, and magnesium oxide. Such an insulating inorganic filler can be used by coating with a resin such as maleimide resin, epoxy resin, polyurethane resin, polyimide resin, polyamide resin, or triazine resin. Among these inorganic fillers, silica (aerosil, spherical silica, etc.) and alumina filler are particularly preferably used because of excellent properties such as insulating properties, environmental stability, and defoaming properties. However, the average diameter of primary particles is prescribed | regulated to 0.001 micrometer-1 micrometer. When the thickness is less than 0.001 μm, the thickening effect is large and the viscosity of the varnish becomes too high, making handling difficult. On the other hand, when it exceeds 1 μm, the defoaming property and thixotropy are lowered.

  Examples of the organic filler include maleimide resin, epoxy resin, polyurethane resin, polyimide resin, polyamide resin, and triazine resin. Of these organic fillers, polyimide resin, maleimide resin, and polyamide resin are particularly preferably used from the viewpoint of heat resistance and solvent resistance. However, the average diameter of the primary particles is specified to be 0.05 μm to 100 μm. When it is less than 0.05 μm, the filler is easily dissolved in the solvent, and it is difficult to maintain the filler dispersion system. On the other hand, when it exceeds 100 μm, the defoaming property, thixotropic property, and uniform dispersibility are lowered.

  Both the inorganic filler and the organic filler need to be insoluble / slightly soluble in the polyimide precursor solution at 50 ° C. or lower in order to have defoaming properties and thixotropic properties. Normally, the temperature during storage and screen printing is preferably 50 ° C. or lower so that the polyimide precursor composition is not denatured and the viscosity is increased. Therefore, the temperature is regulated to 50 ° C. or lower. .

  By dispersing the filler as described above in the polyimide precursor resin composition, the thixotropy and defoaming properties are dramatically improved, and the printing characteristics by screen printing are improved. As a result, a fine polyimide pattern film can be formed. Moreover, since these fillers remain in the thermosetting film, the heat resistance, adhesion, hardness, etc. of the polyimide film can be improved.

  The filler may be used alone or in combination of two or more, but the blending amount is specified to be 3 wt% or more with respect to the polyimide precursor. If the blending amount of the filler is too small, the thixotropy and defoaming properties are insufficient and the printing characteristics are deteriorated, so that a fine polyimide pattern film cannot be formed. In order not to cause deterioration of the insulating properties and dielectric properties of the polyimide pattern film to be obtained, the blending amount of the filler is desirably 50 wt% at the maximum with respect to the polyimide precursor. The blending amount of the filler is more preferably 5 to 20 wt% with respect to the polyimide precursor.

  Considering thixotropy and defoaming properties during screen printing, the filler is preferably an insulating inorganic filler having an average primary particle diameter of 0.001 to 1 μm, particularly from alumina, silica, titanium oxide, or zinc oxide. An insulating inorganic filler of 0.005 to 0.1 μm is desirable.

  The polyimide precursor composition can be prepared by dissolving the above-described components in a predetermined solvent. Examples of the solvent that can be used include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl- 2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether, 1,2-bis ( 2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, 1-acetoxy-2-methoxyethane, 1-acetoxy-2-ethoxyethane, (2-acetoxyethyl) (2-methoxyethyl ) Ether, (2-acetoxyethyl) (2-ethoxyethyl) ether, 3-methoxypro Methyl onate, tetrahydrofuran, 1,3-dioxane, 1,3-dioxolane, 1,4-dioxane, pyrroline, pyridine, picoline, dimethyl sulfoxide, sulfolane, γ-butyrolactone, propylene carbonate, phenol, cresol, cyclohexanone, acetonyl Acetone and the like are exemplified, and these organic solvents may be used alone or in combination of two or more.

  The polyimide precursor composition used in the embodiment of the present invention does not require a dehydrating agent such as carboxylic acid anhydride or DCC (dicyclohexylcarbodiimide), and should not contain a dehydrating agent. When such a dehydrating agent is blended, the polyimide precursor composition gels in a short time, and the storage stability is significantly reduced.

  The stirring method for preparing the polyimide precursor composition is not particularly limited, and a manual stirring method using a spatula or the like, a mechanical stirring method using a mechanical stirrer, a mix rotor, a planetary stirring device, or the like can be employed. .

  The viscosity of the polyimide precursor composition obtained by the method as described above is defined in the range of 50 to 3000 poise. If the viscosity of the polyimide precursor composition is too low, the shape stability during screen printing is insufficient and the pattern tends to deform, and if the viscosity is too high, the coatability during screen printing squeezing is reduced. This is because smears are likely to occur. The viscosity of the polyimide precursor composition is more preferably 100 to 2000 poise.

Further, the polyimide precursor composition was measured using a rotational viscometer of E type (cone / plate method) or B type (cylinder method) (25 ° C. or less), and when the steady shear rate was 20 sec ⁻¹ , And the difference in apparent viscosity shown at 0.5 sec ⁻¹ is large, so that it exhibits remarkable thixotropy. As a value representing the thixotropic thixotropic coefficient [η _0.5 / η _20] (the apparent viscosity [eta _0.5] at steady shear rate 0.5 sec ^-1, the apparent viscosity constant shear rate of 20sec ^-1 [η _20] This value is preferably 1.5 or more for good screen printing characteristics.

  The polyimide precursor composition having thixotropy can form a relief pattern of 0.1 to 100 μm as a film thickness after firing. By setting the degree of polymerization, the viscosity, the concentration, the amount of filler added, and the solid content concentration of the base polymer to be used, it is possible to adjust the viscosity characteristics suitable for the plate shape to be used and the desired film thickness.

The preferred range of the viscosity characteristics of the polyimide precursor composition is roughly 50poise~25000poise is apparent viscosity [eta _0.5] in 0.5 sec ^-1, the apparent viscosity [eta _20] in 20sec ^-1 approximate 10poise~5000poise below is there. When the viscosity is too low ([η _0.5 ] is 50 poise or less or [η ₂₀ ] is 10 poise or less), the shape stability during screen printing is insufficient and the pattern is easily deformed, and the viscosity is too high ([ When [η _0.5 ] is 25000 poise or more or [η ₂₀ ] is 5000 poise or more), the coatability at the time of screen printing squeezing deteriorates and smears, pinholes, etc. are likely to occur.

  By selecting a paste with this viscosity characteristic range, it is possible to obtain plate pattern openings that are highly practical and maintain the shape of the formed relief pattern under appropriate screen printing conditions from thin to thick films. It is done.

  In the method for manufacturing a wiring board according to the embodiment of the present invention, a screen printing method is used for applying the polyimide precursor composition. A polyimide relief film can be formed simply by screen-printing and heat-curing, and the process of applying a polyimide film to form a film and processing it by wet or dry processing after heat-curing has been greatly simplified. Manufacturing cost can be greatly reduced.

  The screen printing method will be described with reference to FIGS.

  First, as shown in FIG. 3, a mesh screen mask 20 is positioned and mounted on the base insulating substrate 11 using a known screen printing apparatus. This positioning can be performed, for example, by performing image recognition. In the mesh screen mask 20, an opening is formed in advance at the position where the electrode portion is formed.

  As the mesh plate, for example, a mesh plate of 40 to 600 mesh can be used. When it is desired to increase the thickness of the polyimide relief film to 10 μm or more, a mesh plate of less than 250 mesh is used. When a high resolution pattern film such as a hole of 200 μm diameter or less is formed, a mesh of 250 mesh or more is used. Use a plate.

  Next, as shown in FIG. 4, the polyimide precursor composition 21 is loaded on the mesh screen mask 20, and the squeegee 22 is moved in the printing direction as shown in FIG. 5. The printing conditions and the like are preferably in a range of a printing squeegee speed of 0.1 to 50 mm / sec, a squeegee angle of 50 to 90 °, and a squeegee hardness of 50 to 100. In addition, the squeegee material includes various polymer-based materials and metal-based materials, but since the solvent used in the polyimide resin precursor composition is a highly soluble polar solvent, the squeegee material used For example, metal or silicon rubber is desirable.

  Thus, the polyimide precursor composition 21 is printed on the base insulating substrate 11 through the mesh screen mask 20.

  As a mask used at the time of screen printing, a polymer-based or metal mesh screen mask and a metal mask are generally used. A metal mesh screen mask or a metal mask is desirable because the solvent used in the polyimide resin precursor composition is a highly soluble polar solvent. By the way, in the screen printing method, printing is performed by scanning a squeegee on a mask, so that printing pressure is applied to the circuit forming surface of the substrate through the mask. Therefore, when the circuit formation surface is very weak, there is a concern that the circuit formation surface may be damaged by the application of the printing pressure.

  For this damage, it is known that the mesh version is more advantageous than the metal version. However, when the inventor performed screen printing of the polyimide precursor composition on the substrate using both the mask of the mesh plate and the metal plate, the influence of the damage due to the type of the mask was not seen. Therefore, when screen-printing a polyimide precursor composition with respect to a board | substrate, the use of both a mesh mask and a metal mask is possible for the kind of mask. Since the solvent used in the polyimide resin precursor composition is a highly soluble polar solvent, the mask material used is preferably a metal mesh mask such as stainless steel or a metal mask.

  As described above, by performing the screen printing process, the polyimide precursor composition is printed except for the formation positions of the electrode portions on the substrate. At this time, in the screen printing method, since the polyimide precursor composition can be collectively disposed at the position where the resin film is disposed on the substrate, the polyimide precursor composition can be disposed efficiently and at low cost. it can.

  In the screen printing method, the film thickness of the polyimide precursor composition to be printed can be easily controlled by the thickness of the mask, and the film thickness of the printed polyimide precursor composition can be easily uniform over the entire surface of the substrate. Can be Therefore, even if it is a polyimide precursor composition film | membrane which requires a comparatively thick dimension of 20-50 micrometers, a predetermined | prescribed film thickness can be easily implement | achieved by using a screen printing method.

  In addition, the screen printing method does not require the wafer to be rotated unlike the conventionally used spin coating method, so the equipment cost can be reduced compared to the spin coating method, and the cost required for film formation is reduced. can do. Further, unlike the potting method, the screen printing method does not cause the polyimide precursor composition to spread over the entire surface of the wafer, and therefore does not cause insufficient wetting.

  By using the screen printing method in this way, fine processing of 50 to 100 μm is possible, and alignment can be performed accurately. In addition, an expensive mold or photomask is not required, and a wiring board can be manufactured using an inexpensive screen mask and printing machine.

  When the screen printing process is completed, the mask is removed from the base insulating base 11 as shown in FIG. 6, and a stationary process for defoaming or leveling of the resin film is performed. Although this time depends on the type of mask to be used, it is about 5 to 60 minutes. Thereafter, the polyimide precursor composition film is changed to a polyimide relief film 23 by heating.

  Heating can be performed in a temperature range of 60 to 300 ° C., for example, in the air or in an inert gas atmosphere. Or you may vacuum-heat at 100-250 degreeC after heating in the temperature range of 60-250 degreeC in the same atmosphere. Due to the low temperature baking, deformation at the time of baking hardly occurs, and a polyimide film pattern excellent in characteristics such as flexibility and adhesion can be obtained.

  As a heating method, heating by a hot plate, heating by an oven, heating by a vacuum dryer, or the like can be employed. The heating time varies depending on the type of polyamic acid and thermosetting accelerator used, the heating temperature, and the film thickness, but 5 minutes to 3 hours is sufficient. By this heat treatment, the solvent component remaining in the coating film volatilizes, and a change to an imide structure occurs due to imidization of the polyamic acid. Further, the thermosetting accelerator is volatilized by evaporation, sublimation, decomposition, etc., and a polyimide composition film 24 as shown in FIG. 7 is formed.

  As described above, according to the method of the embodiment of the present invention, a wiring board can be manufactured at a low cost by a simple process. In addition, since the obtained wiring board does not have an adhesive layer, it can be made thinner / lighter and heat resistance can be improved.

Here, the case where the conventional PEP method is used will be described with reference to FIGS.
In the PEP method, first, as shown in FIG. 8, a polyimide varnish is applied on a printed circuit board 31 and dried to form a polyamic acid film 32. This is baked at a high temperature of 300 ° C. or higher to form a polyimide film 33 as shown in FIG. 9, and then a resist film 34 is deposited as shown in FIG.

  Since a polyimide solid film is formed by high-temperature baking, the substrate is likely to be deformed (curled or the like) during heat curing. Further, due to the difference in thermal expansion coefficient between the substrate and the polyimide film during high-temperature baking, there is a risk that film peeling or film adhesion strength will decrease, and thermal oxidation of copper wiring or the like is likely to occur.

  Further, the resist film 34 is exposed by a conventional method using a UV exposure machine or the like, and developed with, for example, an alkali developer to obtain a resist pattern 35 as shown in FIG. Thereafter, rinsing and drying may be performed as necessary. Using the resist pattern 35 as a mask, the polyimide film 33 is etched with a hydrazone etching solution or the like to form a polyimide film pattern 36 as shown in FIG. At this time, the polyimide film or the wiring layer may be deteriorated. After removing the resist pattern 35 with a resist stripper, rinsing and drying are performed to complete a polyimide film pattern as shown in FIG.

In the case of the PEP method, the manufacturing process is complicated and the manufacturing cost is expensive. In addition, the polyimide film and the wiring layer are easily deteriorated due to high temperature baking or etching.
By using the method according to the embodiment of the present invention, it is possible to avoid all the problems of the conventional manufacturing process, and the obtained wiring board is thin and lightweight and has excellent heat resistance.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.
First, several types of polyimide precursor compositions were prepared by the following method.
Polyimide acid varnish “U-Varnish-A” 20 g made by Ube Industries, Ltd. was mixed and stirred with 1 g of thermosetting accelerator “4-hydroxypyridine” and 0.5 g of silica filler “AEROSIL 200” made by Nippon Aerosil Co., Ltd. A precursor composition (PI-1) was obtained. The polyamic acid varnish used here is obtained by dissolving 4 g of a polyimide precursor in 16 g of N-methyl-2-pyrrolidinone as a solvent. The thermosetting accelerator corresponds to (A1), and its blending amount is about 25 wt% with respect to the polyimide precursor. Moreover, the average diameter of the primary particle of a filler is about 0.012 micrometer, and the compounding quantity is about 12.5 wt% with respect to a polyimide precursor.

The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 1050poise and 260Poise. The thixotropy coefficient was 4.0, and good thixotropy was observed.

  A polyimide precursor is prepared by mixing and stirring 10 g of polyamide acid varnish “Skybond 703” manufactured by Industry Summit Technology Co., Ltd. and 1 g of thermosetting accelerator “4-hydroxypyridine” and 0.5 g of silica filler “AEROSIL200” manufactured by Nippon Aerosil Co., Ltd. A body composition (PI-2) was obtained. The polyamic acid varnish used here is obtained by dissolving 5 g of a polyimide precursor in 5 g of N-methyl-2-pyrrolidinone as a solvent. The thermosetting accelerator corresponds to (A1), and the blending amount is about 20 wt% with respect to the polyimide precursor. Moreover, the average diameter of the primary particle of a filler is about 0.012 micrometer, and the compounding quantity is about 10 wt% with respect to a polyimide precursor.

The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 1240poise and 250Poise. The thixotropy coefficient was 5.0, and good thixotropy was observed.

  A polyimide precursor composition was prepared by mixing and stirring 1 g of a thermosetting accelerator “4-hydroxypyridine” and 0.5 g of silica filler “AEROSIL200” manufactured by Nippon Aerosil Co., Ltd. in 20 g of “Semicofine SP-483” manufactured by Toray Industries, Inc. (PI-3) was obtained. The polyamic acid varnish used here is obtained by dissolving 4 g of a polyimide precursor in 16 g of N-methyl-2-pyrrolidinone as a solvent. The thermosetting accelerator corresponds to (A1), and its blending amount is about 25 wt% with respect to the polyimide precursor. Moreover, the average diameter of the primary particle of a filler is about 0.012 micrometer, and the compounding quantity is about 12.5 wt% with respect to a polyimide precursor.

The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 1060poise and 250Poise. The thixotropy coefficient was 4.2, and good thixotropy was observed.

  A polyimide precursor is prepared by mixing and stirring 1 g of thermosetting accelerator “benzimidazole” and 0.5 g of silica filler “AEROSIL200” manufactured by Nippon Aerosil Co., Ltd. in 20 g of polyamic acid varnish “U-varnish-A” manufactured by Ube Industries, Ltd. A composition (PI-4) was obtained. The polyamic acid varnish used here is obtained by dissolving 4 g of a polyimide precursor in 16 g of N-methyl-2-pyrrolidinone as a solvent. The thermosetting accelerator corresponds to (A1), and its blending amount is about 25 wt% with respect to the polyimide precursor. Moreover, the average diameter of the primary particle of a filler is about 0.012 micrometer, and the compounding quantity is about 12.5 wt% with respect to a polyimide precursor.

The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 1060poise and 260Poise. The thixotropy coefficient was 4.1, and good thixotropy was observed.

  A polyimide precursor is prepared by mixing and stirring 10 g of polyamic acid varnish “Skybond 703” manufactured by Industry Summit Technology with 1 g of thermosetting accelerator “hippuric acid” and 0.5 g of alumina filler “aluminum oxide C” manufactured by Nippon Aerosil Co., Ltd. A body composition (PI-5) was obtained. The polyamic acid varnish used here is obtained by dissolving 5 g of a polyimide precursor in 5 g of N-methyl-2-pyrrolidinone as a solvent. The thermosetting accelerator corresponds to (A2), and the blending amount is about 20 wt% with respect to the polyimide precursor. Moreover, the average diameter of the primary particle of a filler is about 0.013 micrometer, and the compounding quantity is about 10 wt% with respect to a polyimide precursor.

The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 980poise and 250Poise. The thixotropic coefficient was 3.9, and good thixotropic properties were observed.

A polyimide precursor composition (RP-1) was prepared by the same formulation as the above-described composition (PI-1) except that no filler was added. The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 101poise and 92Poise. The thixotropic coefficient was 1.1, and thixotropic property was hardly recognized.

A polyimide precursor composition (RP-2) was prepared by the same formulation as the above-described composition (PI-2) except that no filler was added. The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 103poise and 94Poise. The thixotropic coefficient was 1.1, and thixotropic property was hardly recognized.

A polyimide precursor composition (RP-3) was prepared by the same formulation as the above-described composition (PI-3) except that no filler was added. The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 182poise and 160Poise. The thixotropic coefficient was 1.14, and thixotropic property was hardly recognized.

A polyimide precursor composition (RP-4) was prepared by the same formulation as the above-mentioned composition (PI-4) except that no filler was added. The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 104poise and 95Poise. The thixotropic coefficient was 1.1, and thixotropic property was hardly recognized.

A polyimide precursor composition (RP-5) was prepared by the same formulation as the above-described composition (PI-5) except that no filler was blended. The apparent viscosity of the resulting precursor composition (measurement temperature 25 ° C.), was measured by E-type rotational viscometer at 0.5 sec ^-1 and 20sec ^-1, were respectively 104poise and 98Poise. The thixotropic coefficient was 1.09, and thixotropic properties were hardly recognized.

  Screen printability was evaluated using the polyimide precursor composition described above.

Example 1
Ten screen shots of the polyimide precursor composition (PI-1) were performed on a copper-clad flexible print substrate using a test printing screen mask (stainless steel 200 mesh). Leveling was performed at room temperature for 30 minutes, and a polyimide composition pattern film was formed by a thermosetting process in a program oven at 80 ° C. for 30 minutes, a temperature increase of 20 minutes, and at 200 ° C. for 1 hour.

  The pattern shape of the obtained polyimide composition pattern film was evaluated visually and with an optical microscope. The evaluation is “scratch or sagging defect (the paste spreads in the pattern width direction and the bridging state connected to the adjacent pattern)”, “blur defect (printed smaller than the predetermined size of the print pattern, pattern ) ”,“ Void or chipping ”, and“ Rolling property ”(Poor rotation state when paste flows on the screen in front of the squeegee in the direction of travel of the squeegee in a substantially cylindrical state) Was done. As a result, no defects were observed and the printability was good.

  Moreover, when the cross section of the polyimide composition film pattern was observed with a scanning electron microscope (SEM), it was confirmed that the filler was uniformly dispersed.

(Examples 2 to 10)
A polyimide film pattern is formed and printed in the same manner as in Example 1 except that the polyimide precursor compositions (PI-2), (PI-3), (PI-4), and (PI-5) are used. A test was conducted. As a result of the test, no defect was observed in any of the compositions, and the printability was good. In any case, the filler was uniformly dispersed in the polyimide film pattern.
The adhesion of the cured polyimide composition film prepared in Examples 1 to 5 was evaluated by a gobang eye test. As a result, no film peeling was observed, and the adhesion was good.

(Comparative Examples 1-5)
The same printing test as in Example 1 except that the polyimide precursor compositions (RP-1), (RP-2), (RP-3), (RP-4), and (RP-5) were used. Was done. As a result of the test, a large number of blemishes due to insufficient thixotropy and voids due to insufficient defoaming were observed, and the printability was poor.
When a printed wiring board is produced by screen printing using such a composition, it is easily estimated that good electrical characteristics and durability cannot be obtained.

(Example 6)
Furthermore, a printed wiring board was produced using the polyimide precursor composition and evaluated.
A printed wiring board (FPC) subjected to circuit processing in accordance with JIS-C5016 was prepared as a non-adhesive copper-clad laminate. On this, screen printing of the polyimide precursor composition (PI-1) was performed. Screen printing was performed for 10 shots using a # 200 stainless mesh mask manufactured by Mitani Electronics Co., Ltd., and a sparematic printing machine manufactured by Mino Group, Inc. equipped with a silicon rubber squeegee. Leveling is performed at room temperature for 30 minutes, and a polyimide composition surface protective film (average film thickness: 16 μm) is obtained by a thermosetting process of 30 minutes at 80 ° C., 20 minutes at 200 ° C., and 1 hour at 200 ° C. in a program oven. To form a printed wiring board (FPC).

  The FPC has substantially no curl, and the insulation resistance between lines according to JIS-C5016 is 6 × 10 (15). The adhesion between the protective film and the FPC was firmly adhered without any film peeling by the gobang eye test.

  When the characteristics of the obtained printed wiring board were evaluated, no electrical defects were observed and good characteristics were shown. In addition, the pressure cooker test showed no durability such as film peeling and showed excellent durability.

(Examples 7 to 10)
A printed wiring board was produced in the same manner as in Example 6 except that the polyimide precursor compositions (PI-2), (PI-3), (PI-4), and (PI-5) were used. When the characteristics of the obtained printed wiring board were evaluated, no defects were found and good characteristics were shown. In addition, the pressure cooker test showed no durability such as film peeling and showed excellent durability.

  In the printed wiring board of the example, since there is no adhesive layer between the polyimide composition surface protective film and the substrate, mixing of impurities and the like due to the adhesive can be avoided. As a result, the advantage that the thin film can be reduced in weight can be obtained, and the heat resistance is not lowered by the adhesive layer.

Sectional drawing showing the structure of the wiring board which concerns on one Embodiment of this invention. Sectional drawing showing the structure of the wiring board which concerns on other embodiment of this invention. Sectional drawing showing the process of the manufacturing method of the wiring board concerning one Embodiment of this invention. Sectional drawing showing the process of following FIG. Sectional drawing showing the process of following FIG. Sectional drawing showing the process of following FIG. Sectional drawing showing the process of following FIG. Sectional drawing showing the process of the manufacturing method of the wiring board by PEP method. FIG. 9 is a cross-sectional view illustrating a process following FIG. 8. Sectional drawing showing the process of following FIG. FIG. 11 is a cross-sectional view illustrating a process following FIG. 10. FIG. 12 is a cross-sectional view illustrating a process following FIG. 11. Sectional drawing showing the process of following FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Single-sided board flexible wiring board; 11 ... Base insulation base material; 12 ... Wiring layer 13 ... Insulating layer 14 ... Surface protective film; 15 ... Double-sided board flexible wiring board 16 ... Copper foil; 17 ... Copper plating; DESCRIPTION OF SYMBOLS 21 ... Polyimide varnish for printing; 22 ... Squeegee; 23 ... Polyamide acid pattern film 24 ... Polyimide pattern film; 31 ... Printed circuit board; 32 ... Polyamide acid film 33 ... Polyimide film; 34 ... Resist film; Membrane pattern.

Claims (2)

A substrate;
An insulating layer provided on the substrate and embedded with a wiring layer;
A surface protective film provided on the insulating layer;
At least one of the insulating layer and the surface protective film includes a polyimide resin film containing a filler formed by curing a polyimide precursor, and the filler is hardly soluble in a solution of the polyimide precursor at 50 ° C. or less. The primary particle has an average particle diameter of 0.001 to 1 μm, and / or a resin-coated inorganic filler, and the primary particle has an average particle diameter of 0.05 to 100 μm. Wiring board. A step of applying a polyimide precursor composition having a viscosity of 50 to 3000 poise on a substrate by a screen printing method to form a coating film;
The coating film is heated in the temperature range of 60 to 300 ° C. in the air or in an inert gas atmosphere, or heated in the temperature range of 60 to 250 ° C. and then vacuum-heated in the temperature range of 100 to 250 ° C. to obtain a polyimide resin A method of manufacturing a wiring board comprising a step of forming a film,
The polyimide precursor composition is
A polyimide precursor comprising a polyamic acid having a repeating unit represented by the following general formula (1);

(In the general formula (1), Φ may be the same or different and each represents a tetravalent organic group. Ψ may be the same or different, and each represents a divalent organic group. Indicates an integer.)
A thermosetting accelerator blended in a proportion of 3 wt% or more with respect to the polyimide precursor;
Containing a filler compounded in a proportion of 3 wt% or more with respect to the polyimide precursor,
The thermosetting accelerator comprises an organic compound selected from the following (A1) to (A3),
(A1) A substituted or unsubstituted nitrogen-containing heterocyclic compound having an acid dissociation index pKa (logarithm of the reciprocal of the acid dissociation constant Ka) in an aqueous solution in the range of 0 to 8. (A2) Amino acid compound or N-acyl amino acid compound ( A3) Hydroxy compound represented by the following general formula (2)

(In the general formula (2), Ar ₁ and Ar ₂ may be the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group. Z is the same or different. A carboxy group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an acyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxy group, a mercapto group, a substituted or unsubstituted amino group, or a substituted or unsubstituted amino group. X represents an alkyl group, which may be the same or different and each represents a divalent oxy group, a thio group, a carbonyl group, a carbonylamino group, a carbonyloxy group, a substituted or unsubstituted amino group, an alkyl group, or a polyfluoroalkyl. A represents a group or a single bond, a represents an integer of 0 to 3, b represents an integer of 1 to 5, and c represents an integer of 0 to 5. (The sum of b and c is 2 or more.)
The filler consists of an insulating inorganic filler having an average primary particle diameter of 0.001 to 1 μm and / or an inorganic filler coated with a resin, and an organic filler having an average primary particle diameter of 0.05 to 100 μm. A method for producing a wiring board, which is hardly soluble in a solution of a polyimide precursor at a temperature not higher than ° C.

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