JP3962997B2 - Alkoxy group-containing silane-modified block copolymer type polyamic acid, block copolymerized polyimide-silica hybrid cured product, and metal laminate - Google Patents

Description

The present invention is an alkoxy group-containing silane-modified block copolymer polyamic acid that gives a block copolymer polyimide-silica hybrid cured product having excellent metal adhesion, heat resistance, high elasticity, low thermal expansion, and moderate flexibility; Block copolymerized polyimide-silica hybrid cured product obtained by sol-gel curing and dehydration ring closure of the alkoxy group-containing silane-modified block copolymerized polyamic acid; electrolessly treating the block copolymerized polyimide-silica hybrid cured product The present invention relates to a metal laminate obtained by plating.

In recent years, computerization of parts mounted on personal computers, printers, furniture, automobiles, and the like has progressed, and the provision of particularly inexpensive flexible printed wiring boards has been desired. Also, as portable electronic devices such as mobile personal computers, mobile phones, and IC cards are rapidly spreading, there has been an increasing demand for smaller and higher density electronic circuits.

Polyimide film is generally obtained by ring-closing reaction of polyamic acid synthesized from aromatic tetracarboxylic dianhydride and aromatic diamine, which are synthesized by condensation reaction, and has heat resistance and electrical properties. Excellent and flexible, it is widely used as a substrate material for flexible printed circuit boards (FPC), tape automated bonding (TAB), chip-on-film (COF), chip size package (CSP), etc. Has been.

  In order to use a polyimide film as a substrate material such as FPC, TAB, COF, and CSP, a method of laminating a metal foil with an adhesive such as an epoxy resin on a polyimide film is adopted. Has excellent heat resistance, mechanical strength, electrical characteristics, etc., but the heat resistance of the adhesive is inferior, and therefore the original characteristics of polyimide cannot be fully exhibited. In order to solve such problems, a polyamic acid solution is cast on a metal foil, dried and imidized, and a thermoplastic polyimide is thermocompression bonded without using an adhesive. Laminated bodies (see Patent Document 2), laminated bodies obtained by sputtering an imide film and then electroplating (see Patent Document 3) have been proposed.

However, when a casting method, a thermocompression bonding method, or a sputtering method that does not use an adhesive as described above is employed, a metal foil or roughened imide film having large irregularities is used in order to obtain sufficient adhesion. However, in the future production of fine pitch printed circuit boards, since the smoothness of the interface between the metal layer and the polyimide film is required more severely, both the metal layer and the polyimide film must be smoother. Must be thinner. Moreover, in these precision printed circuit boards, since dimensional stability and adhesion strength after heating are emphasized, it is necessary to further reduce the water absorption rate and thermal expansion coefficient of the polyimide used.

Japanese Patent No. 2746555 Japanese Patent Laid-Open No. 07-193349 Japanese Patent Laid-Open No. 08-330695

  The present invention solves the above problems, that is, even when a casting method for a metal plate or metal foil is employed, an alkoxy group-containing silane-modified block copolymer polyamic acid capable of forming a coating film having high adhesion The purpose is to provide. Another object of the present invention is to provide a polyimide film that is excellent in mechanical strength such as flexibility, has a low water absorption and thermal expansion coefficient, and can be electrolessly plated. In addition, the present invention provides a metal foil laminate having a thin metal layer with excellent adhesion and no interfacial unevenness without using an adhesive, and further a printed circuit board obtained by processing the metal foil laminate. The purpose is to do.

  As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by using a specific alkoxy group-containing silane-modified block copolymer polyamic acid. It came to completion.

That is, in the first aspect of the present invention, a polyamic acid (1) obtained by reacting a tetracarboxylic dianhydride (A) and a diamine (B) is reacted with an epoxy group-containing alkoxysilane partial condensate (2). The resulting silane-modified polyamic acid (I) is further reacted with tetracarboxylic dianhydride (C) and diamine (D) to obtain tetracarboxylic dianhydride (A) and tetracarboxylic dianhydride. 15 to 100 mol% of the total number of moles of product (C) is pyromellitic dianhydride, and 25 to 100 mol% of the total number of moles of diamine (B) and diamine (D) is p-phenylenediamine. it is an alkoxy group-containing silane-modified block copolymer type polyamic acid (However, tetracarboxylic acid dianhydride (a) and the tetracarboxylic dianhydride (C) are identical, and, Zia Excluding those emissions (B) and diamine (D) are identical.) Relates (hereinafter, polyamic acid (II) hereinafter). In the second aspect of the present invention, about 40 to 90 mol% of the total number of moles of diamine (B) and diamine (D) is p-phenylenediamine, and about 10 to 60 mol% is oxadianiline. It relates to the polyamic acid (II) described in the first invention . The third aspect of the present invention is the ratio of (number of moles of tetracarboxylic dianhydride (A)) / (number of moles of diamine (B)) = 1.03 to 1.33 or 0.75 to 0.97. It relates to the polyamic acid (II) according to any one of the first and second inventions, wherein the polyamic acid (1) obtained by reacting is used. 4th of this invention is related with the block copolymerization type polyimide-silica hybrid hardened | cured material obtained by carrying out sol-gel hardening and dehydration ring closure of the polyamic acid (II) in any one of the said 1st- 3rd invention. 5th of this invention is related with the block copolymerization type polyimide-silica hybrid hardened | cured material of the said 4th invention whose water absorption is less than 3%. 6th of this invention is related with the polyamic acid (II) in any one of the 4th or 5th invention containing a filler. Seventh invention, block copolymer type polyimide of the fourth to sixth aspects thermal expansion coefficient is 25ppm or less - about Silica Hybrid cured product. The 8th of this invention is related with the metal laminated body obtained by electroless-plating the block copolymerization type polyimide-silica hybrid hardened | cured material of the said 4th-7th invention.

  According to the polyamic acid (II) of the present invention, a coating film having high adhesion to a metal plate or metal foil can be formed even by a casting method. Moreover, the polyimide-silica hybrid cured product obtained from the polyamic acid (II) of the present invention is excellent in mechanical strength such as flexibility, has a low water absorption and thermal expansion coefficient, and can be electrolessly plated.

The polyamic acid (1) constituting the polyamic acid (II) of the present invention is a resin having a carboxyl group and an amide group in each of adjacent carbon atoms in the amide bond molecular skeleton in the molecule, for example, tetracarboxylic acid A polyamic acid solution obtained by reacting dianhydride and diamine in an organic solvent usually at -20 ° C to 80 ° C can be used. The molecular weight of the polyamic acid (1) is not particularly limited, but preferably has a number average molecular weight of about 1000 to 20000.

Examples of the tetracarboxylic dianhydride used in the polyamic acid (1) constituting the polyamic acid (II) of the present invention include, for example, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride. Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Diphenyl -Tertetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,3, 3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,3 ′, 4,4′-tetracarboxyphenyl) tetrafluoropropane dianhydride, 2,2′-bis (3 , 4-Dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride , Cyclopentanetetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, etc. Acids can be exemplified.

  Further, within the range not losing the effect of the present invention, tricarboxylic acids such as trimellitic anhydride, butane-1,2,4-tricarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, oxalic acid, malonic acid, Aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, vimelic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and their acid anhydrides, isophthalic acid, terephthalic acid, diphenylmethane-4 Aromatic dicarboxylic acids such as 4,4'-dicarboxylic acid and acid anhydrides thereof can be used in combination. However, if these ratios with respect to tetracarboxylic dianhydride are too large, the resulting cured product tends to have poor insulation and heat resistance, so the amount used is usually 30 mol% or less relative to tetracarboxylic acids. It is preferable that

  Examples of the diamine (B) used in the polyamic acid (1) constituting the polyamic acid (II) of the present invention include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diaminophenyl. Methane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-di (m-aminophenoxy) diphenylsulfone, 4,4′-diaminodiphenylsulfide, 1,4-diaminobenzene, 2,5-diaminotoluene, isophoronediamine, 4- (2-aminophenoxy) -1,3-diaminobenzene, 4- (4-aminophenoxy) -1,3-diaminobenzene, 2 -Amino-4- (4-aminophenyl) thiazole, 2-amino-4-phenyl-5- 4-aminophenyl) thiazole, benzidine, 3,3 ′, 5,5′-tetramethylbenzidine, octafluorobenzidine, o-tolidine, m-tolidine, p-phenylenediamine, m-phenylenediamine, 1,2-bis (Anilino) ethane, 2,2-bis (p-aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoropropane, 2,6-diaminonaphthalene, diaminobenzotrifluoride, 1,4-bis (P-aminophenoxy) benzene, 4,4′-bis (p-aminophenoxy) biphenyl, diaminoanthraquinone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluoropropane, 2 , 2-Bis [4- (p-aminophenoxy) phenyl] hexafluoro Examples include diamines such as propane.

In the polyamic acid (1) constituting the polyamic acid (II) of the present invention, the ratio of tetracarboxylic dianhydride (A) and diamine (B) used is not particularly limited, but (tetracarboxylic dianhydride) The value of (the number of moles of (A)) / (the number of moles of diamine (B)) is preferably in the range of 1.03 to 1.33 or 0.75 to 0.97. In the range where the value of (number of moles of tetracarboxylic dianhydride (A)) / (number of moles of diamine (B)) is more than 0.97 and less than 1.03, polyamic acid (1) and epoxy group contained Since the reaction of the alkoxysilane partial condensate (2) is extremely slow, the polyamic acid is imide-closed during the production of the polyamic acid (I), and the polymer tends to become insoluble in an organic solvent, which is not preferable. When the value of (number of moles of tetracarboxylic dianhydride (A)) / (number of moles of diamine (B)) is greater than 1.33 or less than 0.75, polyamic acid (I) is being produced. This is not preferred because it tends to gel. In these, when the storage stability of polyamic acid (1) or polyamic acid (I) is required, (number of moles of tetracarboxylic dianhydride (A)) / (number of moles of diamine (B)) ) Is preferably in the range of 0.75 to 0.97.

The production of the polyamic acid (1) is preferably carried out in an organic solvent that dissolves the polyamic acid (1) and the epoxy group-containing alkoxysilane partial condensate (2) with a polyimide-converted solid residue of 5 to 60%. Here, the polyimide-converted solid residue represents the weight percent of polyimide with respect to the polyamic acid (1) solution when the polyamic acid (1) is completely cured into polyimide. If the polyimide conversion solid residue is less than 5%, the production cost of the polyamic acid (1) solution is increased. On the other hand, when it exceeds 60%, the polyamic acid (1) solution has a high viscosity at room temperature, so that the handling tends to be poor. Examples of the organic solvent to be used include dimethyl sulfoxide, diethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, And organic polar solvents such as N-vinyl-2-pyrrolidone, phenol, o-, m-, or p-cresol, xylenol, halogenated phenol, catechol, hexamethylphosphoramide, γ-butyrolactone, etc. Are preferably used alone or as a mixture, but aromatic hydrocarbons such as xylene and toluene may be used in combination with the polar solvent. Among these, from the viewpoint of the storage stability of polyamic acid (1) and polyamic acid (I), dimethyl sulfoxide, diethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide N, N-diethylacetamide, N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone are preferably used alone or as a mixture.

The reaction temperature of the polyamic acid (1) is not particularly limited as long as the amic acid group remains, but is preferably adjusted to about -20 to 80 ° C. Production below −20 ° C. is uneconomical because the reaction rate is slow and requires a long time, and when it exceeds 80 ° C., the ratio of the amide group in the polyamic acid ring-closing to the imide group increases, and the epoxy group Since the reaction point with the contained alkoxysilane partial condensate (2) tends to decrease, it is not preferable.

  The epoxy group-containing alkoxysilane partial condensate (2) used in the present invention is obtained by a dealcoholization reaction between an epoxy compound having one hydroxyl group in one molecule and an alkoxysilane partial condensate.

  As such an epoxy compound, the number of epoxy groups is not particularly limited as long as it is an epoxy compound having one hydroxyl group in one molecule. In addition, as the epoxy compound, the smaller the molecular weight, the better the compatibility with the alkoxysilane partial condensate, and the higher the heat resistance and adhesion imparting effect. Specific examples thereof include monoglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting epichlorohydrin with water, dihydric alcohol or phenols having two hydroxyl groups; epichlorohydrin; Polyglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting with a trihydric or higher polyhydric alcohol such as glycerin or pentaerythritol; Molecular end obtained by reacting epichlorohydrin with amino monoalcohol Examples thereof include epoxy compounds having one hydroxyl group; alicyclic hydrocarbon monoepoxides having one hydroxyl group in the molecule (for example, epoxidized tetrahydrobenzyl alcohol). Among these, the general formula (1):

What is represented by (p represents the integer represented by 1-13) is preferable, and what is especially p is 1-10 is preferable. Examples of this include, for example, glycidol (trade name “Epiol OH” manufactured by NOF Corporation) and epoxy alcohol (trade name “EOA” manufactured by Kuraray Co., Ltd.). In addition, since the heat resistance of the finally obtained composite cured product tends to decrease when the value of p exceeds 10, for applications where heat resistance is required, the value of p should be 10 or less. Is preferred. Among these epoxy compounds, glycidol and epoxy alcohol are the most excellent in terms of imparting heat resistance, and are most suitable because of their high reactivity with the alkoxysilane partial condensate.

As an alkoxysilane partial condensate,
Formula (2): R ¹ _m Si (OR ² ) _(4-m)
(In the formula, R ¹ represents an alkyl group or aryl group having 8 or less carbon atoms, R ² represents a lower alkyl group having 4 or less carbon atoms, and m represents an integer of 0 or 1.)
A hydrolyzable alkoxysilane monomer represented by the formula (1) is obtained by hydrolyzing in the presence of an acid or base catalyst and water and partially condensing.

  Specific examples of the hydrolyzable alkoxysilane monomer that is a constituent raw material of the alkoxysilane partial condensate include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, Such as methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane And trialkoxysilanes. Among these, since the reactivity with an epoxy compound having one hydroxyl group in one molecule is high, the alkoxysilane partial condensate is synthesized using tetramethoxysilane or methyltrimethoxysilane in an amount of 70 mol% or more. The ones made are preferred.

  In addition, as these alkoxysilane partial condensates, those exemplified above can be used without any particular limitation. However, when two or more of these examples are mixed and used, tetraalkoxysilane in the total amount of the alkoxysilane partial condensate is used. It is preferable to use 70% by weight or more of a methoxysilane partial condensate or a methyltrimethoxysilane partial condensate.

  The number average molecular weight of the alkoxysilane partial condensate is preferably about 230 to 2000, and the average number of Si in one molecule is preferably about 2 to 11. When the average number of Si is less than 2, in the dealcoholization reaction with an epoxy compound having one hydroxyl group in one molecule, the amount of alkoxysilanes flowing out of the system together with alcohol without reacting increases. If it exceeds 11, the reactivity of the epoxy group-containing alkoxysilane partial condensate (2) with the polyamic acid (1) is lowered, and the polyamic acid (I) is hardly obtained.

  The epoxy group-containing alkoxysilane partial condensate (2) can be obtained by dealcoholizing an epoxy compound having one hydroxyl group in one molecule and an alkoxysilane partial condensate. The use ratio of the epoxy compound and the alkoxysilane partial condensate is not particularly limited as long as the alkoxy group remains substantially, but the epoxy group in the resulting epoxy group-containing alkoxysilane partial condensate (2) is not limited. Is usually a charge ratio such that the equivalent of the hydroxyl group of the epoxy compound having one hydroxyl group in one molecule / the equivalent of the alkoxy group of the alkoxysilane partial condensate = 0.01 / 1 to 0.3 / 1. It is preferable to subject the alkoxysilane condensate and an epoxy compound having one hydroxyl group per molecule to a dealcoholization reaction. Since the ratio of the alkoxysilane partial condensate which is not epoxy-modified increases when the charging ratio decreases, the block copolymerization type polyimide-silica hybrid film tends to become opaque. Therefore, the charging ratio is 0.03 or more. / 1 is more preferable. Moreover, since the epoxy group of the epoxy group-containing alkoxysilane partial condensate (2) is polyfunctionalized and becomes easy to gel during synthesis of the polyamic acid (I) when the charging ratio is increased, the charging ratio is 0.3 or less. / 1 is more preferable.

  In the reaction of the alkoxysilane partial condensate and the epoxy compound having one hydroxyl group in one molecule, for example, the above-described components are charged and the alcohol is generated by distilling off the alcohol produced by heating. The reaction temperature is about 50 to 150 ° C., preferably 70 to 110 ° C., and the total reaction time is about 1 to 15 hours. If the dealcoholization reaction is carried out at a temperature exceeding 110 ° C., the molecular weight of the reaction product increases too much with the condensation of alkoxysilane in the reaction system, and there is a tendency to increase the viscosity or gel. In such a case, viscosity increase and gelation can be prevented by a method such as stopping the dealcoholization reaction during the reaction.

  In the dealcoholization reaction of the above alkoxysilane partial condensate and an epoxy compound having one hydroxyl group in one molecule, a conventionally known transesterification catalyst that does not open an epoxy ring is used to promote the reaction. Can be used. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, These oxides, organic acid salts, halides, alkoxides and the like. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate and tin octylate are effective.

  The above reaction can also be carried out in a solvent. As the solvent, if an alkoxysilane condensate and an epoxy compound having one hydroxyl group in one molecule are dissolved and inert to the epoxy group of the epoxy compound having one hydroxyl group in one molecule, There is no particular limitation. Examples of such an organic solvent include dimethyl sulfoxide, diethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2- It is preferable to use a solvent such as pyrrolidone, N-vinyl-2-pyrrolidone, hexamethylphosphoramide, γ-butyrolactone, toluene, xylene.

  The polyamic acid (I) is obtained by reacting the polyamic acid (1) with the epoxy group-containing alkoxysilane partial condensate (2). The ratio of the polyamic acid (1) and the epoxy group-containing alkoxysilane partial condensate (2) used is not particularly limited, but (the equivalent of the epoxy group of the epoxy group-containing alkoxysilane partial condensate (2) / polyamic acid (1) The number of moles of tetracarboxylic dianhydride (A) used in the above is preferably in the range of 0.01 to 0.6. If the above numerical value is less than 0.01, it is difficult to obtain the effect of the present invention, and if it exceeds 0.6, the polyimide-silica hybrid film tends to be opaque, which is not preferable.

  In the production of polyamic acid (I), for example, the above components are charged and the reaction is carried out by heating in a substantially anhydrous state. The main purpose of this reaction is to react the carboxylic acid group of the polyamic acid (1) with the epoxy group of the epoxy group-containing alkoxysilane partial condensate (2). During this reaction, the epoxy group-containing alkoxysilane partial condensate ( It is necessary to suppress the formation of silica due to the sol-gel reaction of the alkoxysilyl moiety of 2). Therefore, the reaction temperature is about 50 to 120 ° C., preferably 60 to 100 ° C., and the reaction time is preferably about 1 to 10 hours.

  In the above dealcoholization reaction, a catalyst used for reacting a conventionally known epoxy group with a carboxylic acid can be used to promote the reaction. Tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methyl Imidazoles such as imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenyl Tetraphenylborate such as phosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate Such as emissions salt can be mentioned. The reaction catalyst is preferably used in a proportion of 0.01 to 5 parts by weight with respect to 100 parts by weight of the solid residue of polyamic acid in terms of polyimide.

  In addition, it is preferable to perform the said reaction in a solvent. The solvent is not particularly limited as long as it dissolves the polyamic acid (1) and the epoxy group-containing alkoxysilane partial condensate (2). As such a solvent, the organic solvent etc. which were used at the time of manufacture of polyamic acid (1) can be illustrated, for example.

  The polyamic acid (II) is obtained by further reacting the polyamic acid (I) with a tetracarboxylic dianhydride (C) and a diamine (D). As tetracarboxylic dianhydride (C), those exemplified as tetracarboxylic dianhydride (A) can be freely selected, and as diamine (D), those exemplified as diamine (B) can be freely selected. Can be used. Tetracarboxylic dianhydride (A) and tetracarboxylic dianhydride (C) may be the same, and diamine (B) and diamine (D) may be the same. Carboxylic dianhydride (A) and tetracarboxylic dianhydride (C) must not be the same, and diamine (B) and diamine (D) must not be the same. Each of these components is composed of a total number of moles of tetracarboxylic dianhydride (A) and tetracarboxylic dianhydride (C) from the viewpoint of water absorption and thermal expansion coefficient of the block copolymerized polyimide-silica hybrid cured product. About 15 to 100 mol% is preferably pyromellitic dianhydride, and about 25 to 100 mol% of the total number of moles of diamine (B) and diamine (D) is preferably p-phenylenediamine. In consideration of flexibility, versatility, and electroless plating adhesion, about 40 to 90 mol% of the total number of moles of diamine (B) and diamine (D) is p-phenylenediamine and about 10 It is particularly preferred that ˜60 mol% is oxadianiline.

The polyamic acid (II) is obtained, for example, by adding a powder of tetracarboxylic dianhydride (C) or diamine (D), a solution or slurry of an organic solvent to the polyamic acid (I), and reacting them. . The method for adding tetracarboxylic dianhydride (C) and diamine (D) is not particularly limited, but tetracarboxylic dianhydride (C) is susceptible to hydrolysis and has poor solubility, so diamine (D) It is preferable to add after the addition. Moreover, when using two or more types of tetracarboxylic acids and diamines for tetracarboxylic dianhydride (C) and diamine (D), they may be added all at once or separately. As in the case of the production of polyamic acid (1), the production of polyamic acid (II) also increases the proportion of the amide acid group in the polyamic acid that cyclizes to the imide group and becomes insoluble in the solvent. Therefore, it is not preferable. The reaction temperature may be determined by the stirring efficiency and the viscosity in the reaction system, but is preferably -20 ° C to 100 ° C for economy and suppression of the imide ring-closing reaction.

The polyamic acid (II) of the present invention comprises a tetracarboxylic dianhydride (A), a diamine (B), a polyamic acid (I) segment composed of an epoxy group-containing alkoxysilane partial condensate (2), and a tetracarboxylic acid. It has a block copolymer structure of a polyamic acid segment not modified with silane composed of an acid dianhydride (C) and a diamine (D). The polyamic acid (I) segment has an alkoxysilane partial condensate in the side chain, forms silica by a sol-gel reaction, and forms intermolecular crosslinks in this silica portion, particularly metal substrate adhesion and electroless plating. Contributes to adhesion. Moreover, the segment of polyamic acid not modified with silane formed from tetracarboxylic dianhydride (C) and diamine (D) does not have silica, and the flexibility of the block copolymerized polyimide-silica hybrid cured product, Or it contributes to the expression of low thermal expansion.

The molecular weight of the polyamic acid (II) is not particularly limited, but is preferably a number average molecular weight of 10,000 to 1,000,000. If the number average molecular weight is less than 10,000, the resulting film becomes brittle. On the other hand, if it exceeds 1,000,000, the viscosity of the polyamic acid (II) becomes too high and handling becomes difficult.

The polyamic acid (II) and the polyamic acid (I) which is an intermediate product thereof have an alkoxy group derived from an alkoxysilane partial condensate in the molecule. Although the content of the alkoxy group is not particularly limited, the alkoxy group is bonded to each other by evaporation of a solvent, heat treatment, or sol-gel reaction or dealcoholization condensation by reaction with moisture (humidity). Since it is necessary to form a cured product, polyamic acid (II) usually holds 50 to 95 mol%, preferably 60 to 90 mol% of the alkoxy group of the alkoxysilane partial condensate unreacted. It is good to keep. The cured product obtained from polyamic acid (II) is
General formula (3): R ¹ _m Si (OR ² ) _{(4-m) / 2}
(In the formula, R ¹ represents an alkyl group or aryl group having 8 or less carbon atoms, R ² represents a lower alkyl group having 4 or less carbon atoms, and m represents an integer of 0 or 1.)
It has the gelatinized fine silica part (high-order network structure of a siloxane bond) shown by these. The polyamic acid (II) is mainly composed of a copolymer type polyamic acid in which a part of the carboxylic acid group derived from the polyamic acid (1) is silane-modified in the polymer chain, but the polyamic acid (II) contains May contain an alkoxysilane partial condensate, an epoxy group-containing alkoxysilane partial condensate (2), an organic solvent or a catalyst used in the reaction. The unreacted alkoxysilane partial condensate and the epoxy group-containing alkoxysilane partial condensate (2) are cured by hydrolysis and polycondensation at the time of curing, and are integrated with the block copolymerized polyimide-silica hybrid cured product. .

When the polyamic acid (II) of the present invention is used for various purposes, the other components are not particularly limited as long as the polyamic acid (II) is contained. The concentration of polyamic acid (II) can be appropriately adjusted with an organic solvent according to the purpose of use. Any organic solvent can be used without particular limitation as long as it can dissolve polyamic acid (II). In addition, when it is necessary to adjust the amount of silica in the cured product for the purpose of adjusting the mechanical strength and heat resistance of the cured product, an alkoxysilane partial condensate or a polyamic acid (1) is added to the polyamic acid (II). It doesn't matter. Also, in order to accelerate hydrolysis and polycondensation when curing the alkoxysilyl moiety of polyamic acid (II), add a small amount of water, organic tin, or organic acid tin-based catalyst to polyamic acid (II). Also good.

When the polyamic acid (II) of the present invention is used for various applications, a filler, a mold release agent, a surface treatment agent, a flame retardant, and a viscosity modifier as long as the effects of the present invention are not impaired. Plasticizers, antibacterial agents, antifungal agents, leveling agents, antifoaming agents, coloring agents, stabilizers, coupling agents, and the like may be blended.

In addition, by using a filler, a friction coefficient can be lowered | hung and film handling can be made easy. Fillers include oxides such as silica, alumina, titania and magnesium oxide, complex oxides such as kaolin, talc and montmorillonite, carbonates such as calcium carbonate and barium carbonate, sulfates such as calcium sulfate and barium sulfate, titanic acid Known materials such as titanates such as barium and potassium titanate, phosphates such as tricalcium phosphate, dicalcium phosphate, and primary calcium phosphate can be used without limitation. In addition, the usage-amount in the case of using a filler is about 0.01 to 50 weight% normally about hardened | cured material, Preferably it is 0.01 to 20 weight.

  The block copolymerized polyimide-silica hybrid cured product of the present invention is obtained by sol-gel curing and dehydration ring closure of polyamic acid (II). The said polyimide-silica hybrid hardened | cured material can be processed into various forms, such as a coating film and a film, with the shaping | molding method. In order to obtain a coating film of a block copolymerization type polyimide-silica hybrid cured product from polyamic acid (II), after coating polyamic acid (II) on a substrate, it is finally cured at about 300 ° C. to 500 ° C. . When the curing temperature is less than 300 ° C., the ring closure reaction from the amic acid group to the imide group becomes incomplete, and when it exceeds 500 ° C., the polyimide-silica hybrid cured product is thermally decomposed depending on the type of polyamic acid. Therefore, it is not preferable. The film-shaped block copolymerization type polyimide-silica hybrid cured product is preferably obtained by cast molding at the above temperature. Examples of the base material used at this time include a metal base material.

In addition, in order to obtain a cured product having a thickness of 10 μm or less using the block copolymerized polyimide-silica hybrid cured product as a coating film or film, the above-described method does not cause a problem, but a thick film cured product exceeding this is produced. When doing so, voids and foaming often occur. Therefore, in order to obtain a cured product having a thickness exceeding 10 μm, it is preferable to set an intermediate temperature at the time of curing the alkoxy group-containing silane-modified block copolymer polyamic acid (II). Specifically, in the case of a coating film, after applying the polyamic acid (II) to the substrate, the organic solvent is dried mainly at a temperature of about 80 to 200 ° C., and the alkoxy in the polyamic acid (II). Silane is subjected to a sol-gel curing reaction to obtain a semi-cured film. Furthermore, the coating film can be obtained by curing the semi-cured film adhered to the substrate at about 300 ° C. to 500 ° C. Similarly, when an impregnated material is obtained, it may be cured in the above two steps after impregnating a substrate such as glass cloth or nonwoven fabric. Moreover, when obtaining a film, it is preferable to peel from a base material as a self-supporting film, and to harden | cure at 300-500 degreeC after 80-200 degreeC drying / curing after casting to a base material.

  The method for obtaining the metal laminate of the present invention is as follows: (i) polyamic acid (II) is cast on a metal plate or metal foil and cured under the above conditions depending on the film thickness (ii) block copolymerized polyimide-silica hybrid cured product The following two can be mentioned: electroless plating. When these metal laminates are used for printed circuit boards, the electroless plating method is preferred because of the advantage that the thickness of the metal layer can be reduced. In particular, when used as FPC, TAB, COF or CSP, it is preferable to prepare a block copolymerized polyimide-silica hybrid cured product with a film thickness of 10 to 60 μm and to perform electroless plating such as copper or nickel. The electroless plating method on the block copolymer polyimide-silica hybrid cured product is not particularly limited, and can be performed by a conventionally known electroless plating method. As an electroless plating method, for example, any method of electroless plating on polyimide films of Examples of Patent Publication No. 262216, Published Patent Publication No. Hei 3-6382, Published Patent Publication No. Hei 6-316768, or Comparative Example However, in this block copolymerization type polyimide-silica hybrid cured product, the electroless plating method on plastics such as ABS and nylon, which has been widely used in the past, can be used. Can be used. Examples of such general-purpose electroless plating methods include “electroless plating, basics and applications” (6th edition, Nikkan Kogyo Shimbun, April 2002, p. 131-144) and “plating textbook” ( 14th Edition, Nikkan Kogyo Shimbun, August 2001, p.233-242). Specific examples of electroless plating on block copolymerized polyimide-silica hybrid cured products include (i) degreasing and washing, (ii) etching with acid or alkali in some cases, and (iii) palladium salts and chelates. And tin salt or the like are adhered to the surface of the block copolymerized polyimide-silica hybrid cured product, and (iv) tin is removed by an acid to exemplify palladium. Further, the thickness of the electroless plating layer is not particularly limited, but it is usually preferably about 0.2 μm to 1.0 μm.

  Moreover, as a metal laminated body of this invention, in order to acquire dimensional stability, it is so preferable that a water absorption is low, and when using for a printed circuit board use especially, the water absorption of a block copolymerization type polyimide-silica hybrid hardened | cured material is 3. It is necessary to adjust to be less than%. From the viewpoint of heat-resistant adhesion, the thermal expansion coefficient of the block copolymerized polyimide-silica hybrid cured product is preferably close to the thermal expansion coefficient of the metal layer. In general, since the thermal expansion coefficient of metal is smaller than that of polyimide, it is preferably 25 ppm or less when used for printed circuit boards.

  As a method for producing a printed board from the metal laminate described above, a conventionally known subtractive method, semi-additive method, or full additive method can be used. In the case of the subtractive construction method, resist printing, exposure, development, and the like are performed by electroplating metal such as copper on a metal foil laminate or electroless plating metal laminate cast on a metal foil. A printed circuit board is produced by a conventionally known method of etching and resist peeling. In the case of the semi-additive construction method, the resist is printed, exposed and developed on the electroless plated metal laminate, and then the electroless plated layer is etched and the resist is peeled off. Further, in the case of the full additive method, resist printing, exposure and development are performed on the block copolymerized polyimide-silica hybrid cured product, electroless plating is performed thereon, and electrolytic plating is further performed. In order to obtain a fine pitch substrate of 50 μm or less, it is preferable to use a semi-additive method or a full additive method among the above methods.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples. In the examples, ODA is oxadianiline, p-PDA is p-phenylenediamine, PMDA is pyromellitic dihydrate, BPDA is 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, NMP Represents N-methyl-2-pyrrolidone, and DMAc represents N, N-dimethylacetamide.

Production Example 1 (Production of epoxy group-containing alkoxysilane partial condensate (1))
In a reactor equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 1400 g of glycidol (trade name “Epiol OH” manufactured by NOF Corporation) and a tetramethoxysilane partial condensate (Tama Chemical Co., Ltd.) Product, trade name “methyl silicate 51”, Si average number 4) 4478.9 g was charged, and 1.1 g of dibutyltin dilaurate was added and reacted in a nitrogen stream. During the reaction, the produced methanol was distilled off using a water separator, and the mixture was cooled when the amount reached about 580 g. The time required for cooling after raising the temperature was 6 hours. Subsequently, about 30 g of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. In this way, an epoxy group-containing alkoxysilane partial condensate was obtained.
In addition, the equivalent of the hydroxyl group of the epoxy compound at the time of preparation / the alkoxy group of the alkoxysilane partial condensate (equivalent ratio) = 0.20, and the epoxy equivalent is 279 g / eq.

Production Example 2 (Production of epoxy group-containing alkoxysilane partial condensate (2))
In a reactor equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 1542 g of glycidol (trade name “Epiol OH”, manufactured by NOF Corporation) and methyltrimethoxysilane partial condensate (Tama Chemical Co., Ltd.) ), Trade name “MTMS-A”, Si average number 3.2) 3476.2 g was charged, and 2.2 g of dibutyltin dilaurate was added and reacted under a nitrogen stream. During the reaction, the produced methanol was distilled off using a water separator, and when the amount reached about 630 g, it was cooled. The time required for cooling after raising the temperature was 6 hours. Subsequently, about 30 g of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. In this way, an epoxy group-containing alkoxysilane partial condensate was obtained.
In addition, the equivalent of the hydroxyl group of the epoxy compound at the time of preparation / the alkoxy group of the alkoxysilane partial condensate (equivalent ratio) = 0.38, and the epoxy equivalent is 209 g / eq.

Production Example 3 (Production of epoxy group-containing alkoxysilane partial condensate (3))
In a reactor equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 1171.1 g of 1-epoxy-8-octanol (manufactured by Kuraray Co., Ltd., trade name “EOA”) and a tetramethoxysilane partial condensate (Tama Chemical Co., Ltd., trade name “methyl silicate 51”, Si average number 4) was charged with 1828.4 g, and 0.6 g of dibutyltin dilaurate was added and reacted in a nitrogen stream. During the reaction, methanol produced using a water separator was distilled off, and the reaction was cooled when the amount reached about 230 g. The time required for cooling after raising the temperature was 6 hours. Subsequently, about 30 g of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. In this way, an epoxy group-containing alkoxysilane partial condensate was obtained.
In addition, the equivalent of the hydroxyl group of the epoxy compound at the time of preparation / the alkoxy group of the alkoxysilane partial condensate (equivalent ratio) = 0.20, and the epoxy equivalent is 337 g / eq.

Example 1 (Production of polyamic acid (3-1))
95.3 g of ODA and 1276.5 g of NMP as diamine (B) were added to a 2 L three-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet tube, and mixed well at room temperature until ODA was completely dissolved. Thereafter, while cooling to 60 ° C. or less, 95.5 g of PMDA was added as tetracarboxylic dianhydride (A) and stirred for 30 minutes to synthesize polyamic acid (1-1). (The number of moles of tetracarboxylic dianhydride (A) / the number of moles of diamine (B)) = 0.92, and the solid residue in terms of polyimide was 12.5%.
Next, the temperature was raised to 80 ° C., 63.9 g of the epoxy group-containing alkoxysilane partial condensate (1) obtained in Production Example 1 was added, and the mixture was stirred at 80 ° C. for 9 hours to give polyamic acid (2-1). Obtained. (Equivalent epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used in polyamic acid (1-1)) = 0.52.
Further, the polyamic acid (2-1) was cooled to 40 ° C., 51.5 g of p-PDA and 340.5 g of NMP were added as the diamine (D), and mixed well until the ODA was completely dissolved. And PMDA111.1g was added as tetracarboxylic dianhydride (C), cooling, and chain extension reaction was performed at 50 degreeC for 1 hour, and polyamic acid (3-1) was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydrides (A) and (C) is 100 mole%, and p-PDA and ODA are 50 moles in the total moles of diamines (B) and (D), respectively. % And 50 mol%.

Example 2 (Production of polyamic acid (3-2))
Add 85.1 g of ODA and 1131.5 g of NMP as diamine (B) to the same apparatus as in Example 1 and mix well at room temperature until ODA is completely dissolved. PMDA 86.7g was added as an anhydride (A), and it stirred for 30 minutes, and synthesize | combined polyamic acid (1-2). (The number of moles of tetracarboxylic dianhydride (A) / the number of moles of diamine (B)) = 0.94, and the solid residue in terms of polyimide was 12.7%.
Next, the temperature was raised to 80 ° C., 63.9 g of the epoxy group-containing alkoxysilane partial condensate (1) obtained in Production Example 1 was added, and the mixture was stirred at 80 ° C. for 10 hours to obtain polyamic acid (2-2). It was. (Equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid (1-2)) = 0.58.
Further, the polyamic acid (2-2) was cooled to 40 ° C., 46.0 g of p-PDA and 485.5 g of NMP were added as the diamine (D), and mixed well until the p-PDA was completely dissolved. And 131.8g of BPDA was added as tetracarboxylic dianhydride (C), cooling, and chain extension reaction was performed at 50 degreeC for 1 hour, and polyamic acid (3-2) was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydrides (A) and (C) is 47 mole%, and p-PDA and ODA are 50 moles in the total number of moles of diamines (B) and (D), respectively. % And 50 mol%.

Example 3 (Production of polyamic acid (3-3))
In the same apparatus as in Example 1, 46.5 g of p-PDA and NMP957.4 g were added as diamine (B), mixed well at room temperature until p-PDA was completely dissolved, and then cooled to 60 ° C. or lower. BPDA 118.3g was added as tetracarboxylic dianhydride (A), and it stirred for 30 minutes, and synthesize | combined polyamic acid (1-3). (The number of moles of tetracarboxylic dianhydride (A) / the number of moles of diamine (B)) = 0.94, and the solid residue in terms of polyimide was 14.1%.
Next, the temperature was raised to 80 ° C., 63.8 g of the epoxy group-containing alkoxysilane partial condensate (1) obtained in Production Example 1 was added, and the mixture was stirred at 80 ° C. for 10 hours to obtain polyamic acid (2-3). Obtained. (Equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid (1-3)) = 0.57.
Furthermore, polyamic acid (2-3) was cooled to 40 ° C., 86.1 g of ODA and 659.7 g of NMP were added as diamine (D), and mixed well until ODA was completely dissolved. And PMDA 99.0g was added as tetracarboxylic dianhydride (C), cooling, and chain extension reaction was performed at 50 degreeC for 1 hour, and polyamic acid (3-3) was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydrides (A) and (C) is 53 mole%, and p-PDA and ODA are 50 moles in the total moles of diamines (B) and (D), respectively. % And 50 mol%.

Example 4 (Production of polyamic acid (3-4))
In the same apparatus as in Example 1, 66.0 g of p-PDA and 1131.5 g of NMP were added as diamine (B), mixed well at room temperature until the p-PDA was completely dissolved, and then cooled to 60 ° C. or lower. As tetracarboxylic dianhydride (A), 165.8 g of BPDA was added and stirred for 30 minutes to synthesize polyamic acid (1-4). (The number of moles of tetracarboxylic dianhydride (A) / the number of moles of diamine (B)) = 0.92, and the solid residue in terms of polyimide was 16.4%.
Next, the temperature was raised to 80 ° C., 63.9 g of the epoxy group-containing alkoxysilane partial condensate (1) obtained in Production Example 1 was added, and the mixture was stirred at 80 ° C. for 8 hours to obtain polyamic acid (2-4). It was. (Equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid (1-4)) = 0.41.
Furthermore, polyamic acid (2-4) was cooled to 40 ° C., 52.4 g of ODA and 485.5 g of NMP were added as diamine (D), and mixed well until ODA was completely dissolved. And PMDA 66.2g was added as tetracarboxylic dianhydride (C), cooling, and chain extension reaction was performed at 50 degreeC for 1 hour, and polyamic acid (3-4) was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydrides (A) and (C) is 35 mole%, and p-PDA and ODA are 70 moles in the total moles of diamines (B) and (D), respectively. %, 30 mol%.

Example 5 (Production of polyamic acid (3-5))
In the same apparatus as in Example 1, 80.7 g of p-PDA and 1453.8 g of diamine (B) were added, mixed well at room temperature until the p-PDA was completely dissolved, and then cooled to 60 ° C. or lower. As tetracarboxylic dianhydride (A), 205.5 g of BPDA was added and stirred for 30 minutes to synthesize polyamic acid (1-5). (The number of moles of tetracarboxylic dianhydride (A) / the number of moles of diamine (B)) = 0.94, and the solid residue in terms of polyimide was 15.7%.
Next, the temperature was raised to 80 ° C., 63.9 g of the epoxy group-containing alkoxysilane partial condensate (1) obtained in Production Example 1 was added, and the mixture was stirred at 80 ° C. for 10 hours to obtain polyamic acid (2-5). It was. (Equivalent epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid (1-5)) = 0.32.
Further, the polyamic acid (2-5) was cooled to 40 ° C., 26.4 g of ODA and 163.2 g of NMP were added as the diamine (D), and mixed well until the ODA was completely dissolved. And PMDA38.1g was added as tetracarboxylic dianhydride (C), cooling, and chain extension reaction was performed at 50 degreeC for 1 hour, and polyamic acid (3-5) was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydrides (A) and (C) is 20 mole%, and p-PDA and ODA are 85 moles in the total number of moles of diamines (B) and (D), respectively. %, 15 mol%.

Example 6 (Production of polyamic acid (3-6))
In the same apparatus as in Example 1, 85.4 g of p-PDA and 974.0 g of DMAc as diamine (B) were added, mixed well at room temperature until the p-PDA was completely dissolved, and then cooled to 60 ° C. or lower. 218.32 g of BPDA was added as tetracarboxylic dianhydride (A) and stirred for 30 minutes to synthesize polyamic acid (1-6). (The number of moles of tetracarboxylic dianhydride (A) / the number of moles of diamine (B)) = 0.94, and the solid residue in terms of polyimide was 21.7%.
Next, it heated up to 80 degreeC, the epoxy group containing alkoxysilane partial condensate (2) 50.7g obtained by manufacture example 2 was added, and it stirred at 80 degreeC for 9 hours, and obtained polyamic acid (2-6). It was. (Equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid (1-6)) = 0.33.
Further, the polyamic acid (2-6) was cooled to 40 ° C., 17.6 g of ODA and 656.9 g of DMAc were added as the diamine (D), and mixed well until the ODA was completely dissolved. And PMDA28.6g was added as tetracarboxylic dianhydride (C), cooling, and chain extension reaction was performed at 50 degreeC for 1 hour, and polyamic acid (3-6) was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydrides (A) and (C) is 15 mole%, and p-PDA and ODA are 90 moles in the total number of moles of diamines (B) and (D), respectively. % And 10 mol%.

Example 7 (Production of polyamic acid (3-7))
In the same apparatus as in Example 1, 81.9 g of p-PDA and 1087.2 g of DMAc as diamine (B) were added, mixed well at room temperature until the p-PDA was completely dissolved, and then cooled to 60 ° C. or lower. As tetracarboxylic dianhydride (A), 209.5 g of BPDA was added and stirred for 30 minutes to synthesize polyamic acid (1-7). (The number of moles of tetracarboxylic dianhydride (A) / the number of moles of diamine (B)) = 0.94, and the solid residue in terms of polyimide was 19.3%.
Next, the temperature was raised to 80 ° C., 78.1 g of the epoxy group-containing alkoxysilane partial condensate (3) obtained in Production Example 3 was added, and the mixture was stirred at 80 ° C. for 7 hours to obtain polyamic acid (2-7). It was. (Equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid (1-7)) = 0.32.
Further, the polyamic acid (2-7) was cooled to 40 ° C., 16.9 g of ODA and 529.3 g of DMAc were added as the diamine (D), and mixed well until the ODA was completely dissolved. And PMDA27.4g was added as tetracarboxylic dianhydride (C), cooling, and chain extension reaction was performed at 50 degreeC for 1 hour, and polyamic acid (3-7) was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydrides (A) and (C) is 15 mole%, and p-PDA and ODA are 90 moles in the total number of moles of diamines (B) and (D), respectively. % And 10 mol%.

Example 8 (Production of silica filler-containing polyamic acid)
10.0 g of polyamic acid (3-5) of Example 5 and 169.9 g of NMP were added to a 250 mL three-necked flask equipped with a stirrer, a cooling pipe, a thermometer, and a nitrogen gas introduction pipe, and polyamic acid (3-5 ) Was thoroughly mixed at room temperature until completely dissolved, then 31.7 g of silica filler (“HDK N 20” manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) was added while cooling to 30 ° C. or lower, and the mixture was stirred for 1 hour. Furthermore, 211.6 g of polyamic acid (3-5) was added to this while cooling to 30 ° C. or lower and stirred for 1 hour to obtain a silica filler-containing polyamic acid.

Comparative Example 1 (Production of alkoxy group-containing silane-modified random copolymer polyamic acid)
Add 46.0 g of p-PDA, 85.1 g of ODA and 1453.8 g of diamine as diamine to the same apparatus as in Example 1, mix well at room temperature until p-PDA and ODA are completely dissolved, then cool to 60 ° C. or lower. While adding 122.3 g of BPDA and 80.4 g of PMDA as tetracarboxylic dianhydride, the mixture was stirred for 30 minutes to synthesize a polyamic acid. (The number of moles of tetracarboxylic dianhydride / the number of moles of diamine) = 0.92, and the solid residue in terms of polyimide was 18.0%.
Next, the temperature was raised to 80 ° C., 63.8 g of the epoxy group-containing alkoxysilane partial condensate (1) of Production Example 1 was added, and the mixture was stirred at 80 ° C. for 7 hours to obtain a silane-modified polyamic acid. (Equivalent epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid) = 0.29.
Further, the silane-modified polyamic acid is cooled to 40 ° C., 163.3 g of NMP is added, 9.6 g of BPDA and 6.3 g of PMDA are added as a tetracarboxylic dianhydride while cooling, and a chain extension reaction is performed at 50 ° C. for 1 hour. Thus, an alkoxy group-containing silane-modified random copolymer polyamic acid was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydride was 47 mole%, and p-PDA and ODA in the total moles of diamine were 50 mole% and 50 mole%, respectively.

Comparative Example 2 (Production of alkoxy group-containing silane-modified polyamic acid)
Add 162.9 g of ODA and NMP1413.4 g as diamine to the same apparatus as in Example 1, mix well at room temperature until ODA is completely dissolved, then cool to 60 ° C. or lower as tetracarboxylic dianhydride. 163.2 g of PMDA was added and stirred for 30 minutes to synthesize polyamic acid. (The number of moles of tetracarboxylic dianhydride / the number of moles of diamine) = 0.92, and the polyimide-converted solid residue was 18.1%.
Next, it heated up to 80 degreeC, the epoxy group containing alkoxysilane partial condensate (1) 62.1g of manufacture example 1 was added, and it stirred at 80 degreeC for 7 hours, and obtained the silane modified polyamic acid. (Equivalent of epoxy group of epoxy group-containing alkoxysilane partial condensate / number of moles of tetracarboxylic dianhydride (A) used for polyamic acid) = 0.18.
Further, the silane-modified polyamic acid is cooled to 40 ° C., 822.5 g of NMP is added, and 13.3 g of PMDA is added as a tetracarboxylic dianhydride while cooling, and a chain extension reaction is performed at 50 ° C. for 1 hour to contain an alkoxy group. A silane-modified polyamic acid was obtained.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydride was 100 mole%, and the number of moles of ODA relative to the total number of moles of diamine was 100 mole%.

Comparative Example 3 (Production of block copolymer type polyamic acid)
To the same apparatus as in Example 1, 96.0 g of ODA and 1640.0 g of NMP were added as diamines, mixed well at room temperature until ODA was completely dissolved, and then cooled to 60 ° C. or lower as tetracarboxylic dianhydride. 97.8 g of PMDA was added and stirred for 30 minutes to synthesize polyamic acid. (The number of moles of tetracarboxylic dianhydride / the number of moles of diamine) = 0.94, and the solid residue in terms of polyimide was 10.2%.
Next, the polyamic acid was cooled to 40 ° C., 51.8 g of p-PDA was added as a diamine, and mixed well until the p-PDA was completely dissolved. Then, 148.7 g of BPDA was added as a tetracarboxylic dianhydride while cooling, and a chain extension reaction was performed at 50 ° C. for 1 hour to obtain a block copolymer type polyamic acid.
The number of moles of PMDA relative to the total number of moles of tetracarboxylic dianhydride was 47 mole%, and the number of moles of p-PDA and ODA relative to the total number of moles of diamine were 50 mole% and 50 mole%, respectively.

(Adhesion)
Polyamic acid (II) of Examples 1 to 7, silica filler-containing polyamic acid of Example 8, alkoxy group-containing silane-modified random copolymer polyamic acid of Comparative Example 1, alkoxy group-containing silane-modified polyamic acid of Comparative Example 2, The block copolymer polyamic acid of Comparative Example 3 was applied to a glass plate and a copper plate so as to have a film thickness of 10 μm, and cured at 150 ° C. for 30 minutes and at 300 ° C. for 30 minutes to form a polyimide-silica hybrid cured product. It was. The block copolymer polyamic acid of Comparative Example 3 was also formed with polyimide by the same method as described above. A gobang eyes cellophane tape peeling test was conducted according to a general test method of JIS K-5400, and the following criteria were used. The evaluation results are shown in Table 1.
A: 100 to 90/100
X: 89-0 / 100

From Table 1, it can be seen that high adhesion can be obtained by silane modification in all Examples and Comparative Examples 1 and 2, whereas Comparative Example 3 does not show any adhesion.

Examples 9 to 16 and Comparative Examples 4 to 6 (Production of cured polyimide)
The polyamic acid (II) of Examples 1 to 7 and the silica filler-containing polyamic acid of Example 8 were cast on a glass plate, dried at about 120 ° C. for 10 minutes, and then the semi-cured film was peeled off from the glass plate. The semi-cured film was fixed to a support frame, and then heated at 200 ° C. for about 10 minutes and at 400 ° C. for 10 minutes to obtain a block copolymer type polyimide-silica hybrid film of about 25 μm. In the same manner as above, the silica filler-containing polyamic acid of Example 8, the alkoxy group-containing silane-modified random copolymer polyamic acid of Comparative Example 1, the alkoxy group-containing silane-modified polyamic acid of Comparative Example 2, and the comparative example 3 A corresponding polyimide film was obtained from the block copolymer type polyamic acid.

(Film physical properties)
Table 2 shows the linear expansion coefficient and water absorption of the films obtained in Examples 9 to 16 and Comparative Examples 4 to 6.

１）測定装置（商品名 ＴＭＡ１２０Ｃ、セイコー電子工業製）により測定した１００〜２５０℃の熱膨張係数
２）ＪＩＳ Ｃ−６４８１の吸水率測定方法により測定した吸水率

1) Coefficient of thermal expansion at 100 to 250 ° C. measured with a measuring device (trade name: TMA120C, manufactured by Seiko Denshi Kogyo Co., Ltd.) 2) Water absorption measured by the water absorption measuring method of JIS C-6481

From Table 2, it is clear that compared with Comparative Examples 4 and 5, the Examples exhibit low thermal expansion.

The films obtained in Examples 9 to 16 and Comparative Examples 4 to 6 were cut out with dumbbell No. 1, and using a Tensilon tester (trade name UCT-500, manufactured by Orientec Co., Ltd.) at a pulling speed of 500 mm / min. The film was stretched and the film elongation until breaking and the strength and elastic modulus at break were measured. A tensile test was performed three times at 25 ° C. in the same manner, and the average value is shown in Table 3.

From Table 3, it can be seen that the elastic modulus of Example 10 is higher than that of Comparative Examples 4 and 6.

Examples 17-24, comparative examples 7-9 (manufacture of a metal laminated body)
The film obtained in Examples 9 to 16 and Comparative Examples 4 to 6 is described in “Electroless plating, basics and applications” (6th edition, Nikkan Kogyo Shimbun, April 2002, p. 233 to 242). By this method, electroless nickel plating was performed to obtain a polyimide film with nickel having a thin nickel plating layer having a thickness of 0.5 μm. Furthermore, 25-micrometer electrolytic copper plating was given to the obtained polyimide film with nickel, and the metal laminated body which has a 0.5-micrometer nickel layer and a 25-micrometer copper layer on the polyimide film was obtained.

(Plating adhesion)
About the metal laminated body of Examples 17-24 and Comparative Examples 7-9, 90 degree peel strength was measured and it showed by the average value.

From Table 4, it can be seen that high adhesion can be obtained by silane modification in all Examples and Comparative Examples 7 and 8, whereas Comparative Example 9 does not show any adhesion.

    The polyamic acid (II) and filler-containing polyamic acid of the present invention can be used as a heat resistant coating agent. Moreover, the block copolymerization type polyimide-silica hybrid cured product obtained by curing the polyamic acid (II) and filler-containing polyamic acid is extremely useful as a substrate for FPC, TAB tape, COF, and CSP. Moreover, the metal laminated body formed by electroless-plating the said block copolymerization type polyimide-silica hybrid hardened | cured material is useful as a laminated board for printed circuit boards.

Claims (8)

Silane-modified polyamic acid (I) obtained by reacting polyamic acid (1) obtained by reacting tetracarboxylic dianhydride (A) and diamine (B) with epoxy group-containing alkoxysilane partial condensate (2) ) Is further obtained by reacting tetracarboxylic dianhydride (C) and diamine (D), and the total number of moles of tetracarboxylic dianhydride (A) and tetracarboxylic dianhydride (C). An alkoxy group-containing silane-modified block copolymer in which 15 to 100 mol% is pyromellitic dianhydride and 25 to 100 mol% of the total number of moles of diamine (B) and diamine (D) is p-phenylenediamine. polymerizable polyamic acid (However, tetracarboxylic acid dianhydride (a) and the tetracarboxylic dianhydride (C) are identical, and a diamine (B) and diamine (D) Except for those that are the same.). Total moles 40-90 mole% of the diamine (B) and diamine (D) is, p- a phenylenediamine and 10 to 60 mole percent, an alkoxy group of claim 1 Symbol placement oxa dianiline Containing silane-modified block copolymerized polyamic acid. (Number of moles of tetracarboxylic dianhydride (A)) / (Number of moles of diamine (B)) = 1.3-1.33 or 0.75-0.97 polyamic acid obtained by reaction The alkoxy group-containing silane-modified block copolymer polyamic acid according to claim 1 or 2 , wherein (1) is used. A block copolymerized polyimide-silica hybrid cured product obtained by subjecting the alkoxy group-containing silane-modified block copolymerized polyamic acid according to any one of claims 1 to 3 to sol-gel curing and dehydration ring closure. The block copolymer-type polyimide-silica hybrid cured product according to claim 4 , wherein the water absorption is less than 3%. The block copolymer-type polyimide-silica hybrid cured product according to claim 4 or 5 containing a filler. The polyimide-silica hybrid cured product according to any one of claims 4 to 6 , having a thermal expansion coefficient of 25 ppm or less. Claims 4-7 block copolymer polyimide according to any one of - Silica Hybrid cured electroless plating and metal obtained laminate.