JP2005146213A - Method for producing silane-modified polyimide siloxane resin containing methoxysilyl group, the resin, the resin composition, cured film, and metal foil laminated product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silane-modified polyimide siloxane resin which can keep high heat resistance and insulation, the intrinsic properties of a polyimide resin, is improved in adhesiveness to metal foil and water absorption, and can be cured to give so little a shrinkage that a cured film may be produced to be free from curving. <P>SOLUTION: The method for producing a silane-modified polyimide siloxane resin containing a methoxysilyl group comprises an esterification reaction for ring closure of (A) an organic solvent-soluble polyimide siloxane resin and (B) an epoxy group-containing methoxysilane partial condensation product, wherein the organic solvent-soluble polyimide siloxane resin can be obtained by reacting (a1) a tetracarboxylic acid dianhydride, (a2) dihydroxy siloxane, and (a3) a diamine, has at least a carboxy group and/or an acid anhydride group at its molecular end of the side chain, and has an imide ring closure rate of 90% or more; and the epoxy group-containing methoxysilane partial condensation product can be obtained by reacting for demethanolation of (b1) an epoxy alcohol and (b2) a methoxysilane partial condensation product. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a methoxysilyl group-containing silane-modified polyimidesiloxane resin, a resin obtained by the production method, a composition containing the resin, and a metal foil laminate using the resin composition. The cured film obtained from the methoxysilyl group-containing silane-modified polyimidesiloxane resin or the resin composition of the present invention is an electric insulating material such as a wire coating agent, a semiconductor interlayer insulating material, a coating agent for build-up substrates, a resist ink, a conductive paste, etc. Useful as. Moreover, the metal foil laminated body of this invention is suitable as a copper-clad board for flexible printed circuit boards, a TAB tape, and a COF tape.

  In recent years, downsizing and increasing the density of circuit boards used in electrical appliances and electronic devices have been demanded due to miniaturization of internal components accompanying the reduction in the thickness and size of electrical appliances and electronic devices. In order to realize miniaturization and high density of a circuit, a material excellent in various physical properties such as electrical properties, for example, heat resistance, insulation, low curling property, adhesion to copper foil, and the like is required.

  A polyimide resin is known as a material excellent in heat resistance, flexibility, electrical insulation, and the like, but most of the polyimide resin does not dissolve in a solvent. Moreover, since the polyimide film obtained from a polyimide resin is inferior in adhesiveness with metal conductors, such as copper foil, the method of making it adhere | attach with a metal conductor normally through adhesive layers, such as an epoxy-type adhesive agent, is employ | adopted. However, since the adhesive has inferior physical properties as compared with the polyimide resin, a technique capable of directly bonding the polyimide resin to the metal conductor is required. As the direct bonding method, there is a method of roughening the copper foil and applying and curing polyamic acid which is a precursor of the polyimide resin. However, in this method, the adhesion to the copper foil is insufficient, There is a disadvantage that water is generated when the acid is cured to form a polyimide resin, so that curing shrinkage occurs and the metal foil laminate curls. On the other hand, an organic solvent-soluble polyimide resin of a type in which imidization is completed in an organic solvent is also known, but the metal foil laminate is slightly due to shrinkage that occurs when the solvent volatilizes and the difference in thermal expansion from the copper foil. However, warping occurs. In addition, the organic solvent-soluble polyimide resin cannot satisfy the high heat resistance required recently in the field of electronic materials, and therefore cannot satisfactorily form a high-performance and fine printed circuit.

  Although a polyamic acid solution is applied to a copper foil without using an adhesive having inferior heat resistance, drying, imidization, or a polyimide base material with a thermoplastic polyimide resin thermocompression-bonded has been studied. Since the copper foil laminate of polyimide resin obtained by the method has low adhesive strength, it is difficult to use for copper foil with small unevenness (small surface roughness) required for fine pitch and high frequency response, In addition, it has been pointed out that the heat resistance is impaired. Moreover, when using polyamic acid, there also exists a problem that hardening shrinkage arises at the time of imidation and a copper foil laminated body warps.

  In order to solve these problems, (1) a method of adding a filler to polyimide or polyamic acid, and (2) an organic-inorganic hybrid material in which polyimide or polyamic acid and an organic silane compound are combined are proposed. (See Patent Document 1). The present applicant has already developed an organic-inorganic hybrid material excellent in heat resistance, insulation, copper foil adhesion, etc. by causing a ring-opening esterification reaction between polyimide or polyamic acid and a specific alkoxysilane partial condensate. (See Patent Document 2). However, the conventional polyimide-based organic-inorganic hybrid material obtained from polyamic acid can satisfy the adhesiveness to the copper foil, but water is generated by the imide ring-closing reaction at the time of heat-curing, so that the curing shrinkage increases, Since warpage tends to occur, it is not necessarily suitable as a material for a circuit board.

Japanese Patent No. 2760520 WO 01/005862 pamphlet

  The present invention improves the adhesiveness and water absorption rate to the metal foil while maintaining the high heat resistance and insulation properties that are the original performance of the polyimide resin, and can provide a cured coating that has very little curing shrinkage and no warpage. It aims at providing the manufacturing method of the silane modified polyimide siloxane resin, the said resin, the said resin composition, the cured film obtained using the said resin composition, and a metal foil laminated body.

  The present inventor has intensively studied to solve the above problems, and by using a specific methoxysilyl group-containing silane-modified polyimidesiloxane resin or a resin composition thereof, a cured product or a metal foil laminate that can solve the above problems. It was found that a body was obtained, and the present invention was completed.

  That is, the present invention is a polyimide siloxane resin soluble in an organic solvent obtained by reacting tetracarboxylic dianhydride (a1), diamines (a2), and dihydroxysiloxane (a3), at the molecular end. Those having a carboxyl group and / or an acid anhydride group, each having a carboxyl group in the side chain and the imide ring closure rate of 90% or more, an epoxy alcohol (b1) and a methoxysilane partial condensate ( The present invention relates to a process for producing a methoxysilyl group-containing silane-modified polyimidesiloxane resin, characterized by subjecting an epoxy group-containing methoxysilane partial condensate (B) obtained by removing methanol from b2) to a ring-opening esterification reaction. The present invention also relates to a methoxysilyl group-containing silane-modified polyimidesiloxane resin obtained by the production method. Moreover, this invention relates to the cured film characterized by hardening the said resin or the said resin composition. Furthermore, this invention relates to the metal foil laminated body characterized by apply | coating the said resin composition on metal foil, and making it heat-harden then.

  When the methoxysilyl group-containing silane-modified polyimidesiloxane resin or the resin composition of the present invention is used, the adhesive property to the metal foil and the low water absorption are maintained while maintaining the high heat resistance and insulation properties that are the original performance of the polyimide resin. It can provide a cured film that is excellent and has very little curing shrinkage and no warpage. Therefore, according to the present invention, there is a specific effect that a metal foil laminate having such various characteristics can be provided.

  The polyimidesiloxane resin (A) (hereinafter referred to as the resin (A)) having an imide ring closure rate of 90% or more used in the present invention is a resin having an imide bond at the specific ratio in the molecule. The modified polyimide resin is prepared such that a carboxyl group and / or an acid anhydride group is present at the terminal and a carboxyl group is present in the side chain, and is soluble in various organic solvents described later. In the resin composition of the present invention, the resin (A) is used as an essential component. When the imide ring closure rate is less than 90%, the curing shrinkage is increased, and the metal foil laminate obtained by using this is not preferable because warpage based on the curing shrinkage occurs.

  The resin (A) is obtained by heating tetracarboxylic dianhydride (a1) (hereinafter referred to as component (a1)) and dihydroxysiloxane (a2) (hereinafter referred to as component (a2)) in an organic solvent. After making a modified siloxane having a carboxyl group and / or an acid anhydride group at both ends by ring-opening ester reaction, diamines (a3) (hereinafter referred to as component (a3)) and, if necessary, component (a1) Is added and heated to cause imidization reaction.

  The constituent raw materials of the resin (A) are the component (a1), the component (a2) and the component (a3) as described above. Specific examples of the component (a1) include pyromellitic acid anhydride, 1,2,3,4-benzenetetracarboxylic acid anhydride, 1,4,5,8-naphthalenetetracarboxylic acid anhydride, 2,3, 6,7-naphthalenetetracarboxylic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 , 3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetra Carbo Acid 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 anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic anhydride, etc. These are used singly or in combination of two or more.

  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 the tetracarboxylic acids are too large, the insulating properties and heat resistance of the resulting cured product tend to be lowered, so the amount used is usually 30 mol% or less with respect to the tetracarboxylic acids. It is preferable.

  Component (a2) is a polymer compound having an alkyl group or a phenyl group directly bonded to a silicon atom and having a hydroxyl group at the molecular end of a polysiloxane having a siloxane bond as a continuous unit. As the component (a2), for example, the general formula (1):

The compound represented by these is mentioned. In general formula (1), R ¹ is a methylene group or phenylene group having 2 to 6 carbon atoms, independently of each other, preferably a methylene group having 3 to 5 carbon atoms. R ² independently represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and the number of repeating units n is about 3 to 30, preferably 3 to 20. If the number of n is less than 3, warping tends to occur, and if the number of n exceeds 20, the solubility in organic solvents tends to decrease. Specific examples of the component (a2) include α, ω-bis (2-hydroxyethyl) polydimethylsiloxane, α, ω-bis (3-hydroxypropyl) polydimethylsiloxane, α, ω-bis (4-hydroxybutyl). ) Polydimethylsiloxane, α, ω-bis (5-hydroxypentyl) polydimethylsiloxane, α, ω-bis [3- (2-hydroxyphenyl) propyl] polydimethylsiloxane, α, ω-bis [3- (4 -Hydroxyphenyl) propyl] polydimethylsiloxane and the like, and these are used alone or in combination of two or more. Of these, α, ω-bis (3-hydroxypropyl) polydimethylsiloxane with high versatility (Dow Corning Asia Co., Ltd. Paintad 8579, DK X8-8579-4, Asahi Kasei Wacker Silicone Co., Ltd. IM-11) It is more preferable to use.

  The amount of component (a2) used in the resin (A) is preferably 1% or more and less than 70%. If it is less than 1%, the flexibility tends to decrease, and if it is 70% or more, the cured film surface tends to have tack. Furthermore, in order to use the metal foil laminated body of this invention as a flexible printed circuit board, it is preferable that said value shall be about 5 to 30%.

  As component (a3), p-phenylenediamine, m-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'- Diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2-di (3 -Aminophenyl) propa 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1,1,1 , 3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) ) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,4-bis 3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4- Bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino) -Α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1, 3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3 -Amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-aminophenoxy) benzonitrile, 2 , 6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) Phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-Aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3 Aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4 -Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- ( 4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] Benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4, 4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4 -(4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-di Mino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxy Benzophenone, 6,6′-bis (3-aminophenoxy) 3,3,3,3,3′-tetramethyl-1,1′-spirobiindane 6,6′-bis (4-aminophenoxy) 3,3 3, '3,3'-tetramethyl-1,1'-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α , Ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether Bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3 -Aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, , 2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, Ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopen 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4 -Di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] Heptane and the like can be exemplified, and these are used alone or in combination of two or more.

  In addition to the above diamines, the component (a3) includes triamines and tetraamines such as 3,4,4′-triaminodiphenyl ether and 2,3,6-triaminopyridine, and the effects of the present invention are lost. Can be used in a range that is not. By using the triamines and tetraamines, a branched structure can be imparted to the resin (A) to be generated, and the terminal carboxyl group and / or acid anhydride of the resin (A) molecule due to the branched structure. The group can be increased. Therefore, the reaction point with the epoxy group-containing methoxysilane partial condensate (2) can be increased.

  Moreover, the polyimide adduct body whose molecular terminal is a carboxylic anhydride group or an amino group which is a reaction product of the said tetracarboxylic acid and diamine can also be used as 1 type of tetracarboxylic acid or diamine.

As described above, the resin (A) is composed of the component (a1), the component (a2), and the component (a3). By adding these components simultaneously or sequentially and reacting them, the resin (A) can be obtained, but the reaction process is presumed as follows. That is, the hydroxyl group present at the molecular end of the component (a2) reacts with the acid anhydride group of the component (a1) to form an ester bond, and at the same time, a so-called half-esterification reaction that generates a carboxyl group. The amino group of component (a3) reacts with an acid anhydride group derived from excess component (a1) to form an imide bond. Accordingly, the resin (A) has a carboxyl group and / or an acid anhydride group derived from an excess component (a1) at the molecular end, and a carboxyl group generated by a half-esterification reaction in the side chain. It will be a thing.

  As a more specific production method of the resin (A), the component (a2) and the component (a1) are reacted in an organic solvent at a reaction temperature of about 80 to 160 ° C., preferably 100 to 150 ° C., and the reaction time is 0.5 to A half-esterification reaction is carried out for about 5 hours, preferably 0.5 to 3 hours to produce a double-terminal acid anhydride siloxane. Next, the polyamic acid is reacted by reacting the both terminal acid anhydride siloxane and the component (a3), and in some cases the insufficient component (a1) in a polar solvent at about 0 to 80 ° C. for about 30 minutes. To manufacture. The polyamic acid dehydration ring-closing reaction may be performed at about 80 to 250 ° C., preferably 100 to 200 ° C., and the reaction time is about 0.5 to 50 hours, preferably 1 to 20 hours. In this dehydration ring closure reaction, a dehydrating agent and a catalytic amount of a tertiary amine such as tertiary amine or pyridine may be used. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides, and the like. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. As said polar solvent used for manufacture of the said resin (A), what is necessary is just to melt | dissolve resin (A) to produce | generate, and a kind and usage-amount are not specifically limited. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, cresol, dimethyl sulfoxide, N-methylcaprolactam, methyltriglyme, methyldiglyme, benzyl alcohol and the like are preferable. Among these organic solvents, N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide are easily compatible with the resin (A) and the epoxy group-containing methoxysilane partial condensate (B). Since it can use as it is as a solvent for reaction, it is especially preferable.

  In the dehydration cyclization reaction of the resin (A), it is important to proceed so that the dehydration cyclization reaction rate is 90% or more so that the remaining amount of the amic acid bond is as small as possible. If the reaction rate is less than 90%, the finally obtained metal foil laminate is likely to be warped and the water absorption rate is increased, which is not preferable for printed circuit board applications.

  In the above reaction, the ratio of each of the component (a1), the component (a2), and the component (a3) is [number of moles of (a1)] / [number of moles of (a2) + number of moles of (a3)] = It is preferable that it is 1.0-1.2. If the ratio is less than 1.0, the residual amount of the unreacted component (a1) increases, and the reactivity of the resulting resin (A) with respect to the epoxy group-containing methoxysilane partial condensate (B) tends to decrease. is there. Moreover, when the ratio exceeds 1.2, the flexibility of the obtained cured film tends to be reduced. Furthermore, the component ratio of the component (a2) in the resin (A) is preferably 1% or more and less than 70%. If it is less than 1%, the resulting metal foil laminate tends to warp, and if it exceeds 70%, the resulting cured film tends to be tacky. The composition ratio is more preferably 3% or more in consideration of the mechanical strength of the cured film, and more preferably less than 40% in consideration of solvent solubility.

  The epoxy group-containing methoxysilane partial condensate (B) used in the present invention comprises an epoxy alcohol (b1) (hereinafter referred to as component (b1)) represented by the general formula (2), and a methoxysilane partial condensate. It is obtained by a demethanol reaction with (b2) (hereinafter referred to as component (b2)).

（式中、ｍは１〜１０の整数を表す。）で表される化合物を用いることが、得られる硬化膜の柔軟性が向上するため好ましい。なお、一般式（２）においてｍが３以上のものを用いた場合には毒性が低くなり、かつ硬化膜の柔軟性の向上が著しいため特に好ましい。 The component (b1) is not particularly limited as long as it has an epoxy group and a hydroxyl group in the molecule, and a known component can be used. As the component (b), usually
General formula (2):

It is preferable to use a compound represented by the formula (wherein m represents an integer of 1 to 10) because the flexibility of the resulting cured film is improved. In addition, it is particularly preferable to use a compound having m of 3 or more in the general formula (2) because the toxicity becomes low and the flexibility of the cured film is remarkably improved.

As the component (b2), general formula (1): Si (OCH ₃ ) ₄
A hydrolyzable methoxysilane monomer represented by the formula (1) is hydrolyzed in the presence of an acid or base catalyst and water and partially condensed.

  The average number of Si in one molecule of the component (b2) is preferably about 2 to 100, and more preferably 3 to 8. When Si is less than 2, during the demethanol reaction with component (b1), the amount of methoxylanes that do not react and flows out of the system together with methanol tends to increase. Moreover, when it exceeds 100, the reactivity with a component (b1) tends to worsen, and it becomes difficult to obtain the target epoxy-group-containing methoxysilane condensate (B).

  The proportion of component (b1) to component (b2) used is not particularly limited, but usually (equivalent of methoxy group in component (b2)) / (equivalent of hydroxyl group in component (b1)) = 1 / It is preferable to carry out demethanol reaction at a charge ratio of about 0.3 to 1 / 0.01.

  In the above charging ratio, when the ratio increases, the ratio of the unreacted component (b2) increases, and when the ratio decreases, the remaining unreacted component (b1) tends to deteriorate the heat resistance of the cured product. Therefore, the charging ratio is more preferably 1 / 0.25 to 1 / 0.05.

  The reaction of the component (b1) and the component (b2) is carried out, for example, while charging each component and heating and distilling off methanol produced as a by-product. The reaction temperature is about 50 to 150 ° C, preferably 70 to 110 ° C. In addition, when the methanol removal reaction is performed at a temperature exceeding 110 ° C., the molecular weight of the reaction product tends to increase too much and the viscosity of the reaction product tends to increase due to the condensation of the component (b2) in the reaction system. In such a case, viscosity increase and gelation can be prevented by a method such as stopping the methanol removal reaction during the reaction.

  In addition, when the methanol removal reaction between the component (b1) and the component (b2) is performed, a conventionally known catalyst that does not open the oxirane ring can be used to promote the reaction. Examples of the catalyst include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, cadmium, and manganese. Metals: These metal oxides, organic acid salts, halides, alkoxides and the like. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin laurate, tin octylate and the like are effective.

  Moreover, the said reaction can also be performed in a solvent. The solvent is not particularly limited as long as it can dissolve the component (b1) and the component (b2). As such an organic solvent, it is preferable to use an aprotic polar solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, and xylene.

  In addition, it is not necessary for all the molecules constituting the epoxy group-containing methoxysilane partial condensate (B) to contain an epoxy group, as long as it contains an epoxy group having the above ratio. That is, the partial condensate (B) may contain an unreacted component (b2) up to about 20% by weight.

  The methoxysilyl group-containing silane-modified polyimidesiloxane resin of the present invention comprises a carboxyl group and / or an acid anhydride group present at the terminal or side chain of the resin (A) molecule and an epoxy group-containing methoxysilane partial condensate (B). Obtained by reacting with. This reaction is mainly a ring-opening esterification reaction of the oxirane ring that occurs between the carboxyl group and / or acid anhydride of the resin (A) and the epoxy group of the epoxy group-containing methoxysilane partial condensate (B). is there. Here, the methoxysilyl group itself of the epoxy group-containing methoxysilane partial condensate (B) may be consumed by moisture or the like present in the reaction system, but usually does not participate in the ring-opening esterification reaction. Therefore, usually, methoxysilyl groups remain in the silane-modified polyimidesiloxane resin by 60% or more. It is preferable to leave 80% or more of the methoxysilyl group.

  The methoxysilyl group-containing silane-modified polyimidesiloxane resin is produced by charging the resin (A) and the epoxy group-containing methoxysilane partial condensate (B) and heating them to cause a ring-opening esterification reaction. The reaction temperature is usually about 40 to 130 ° C, preferably 70 to 110 ° C. If the reaction temperature is less than 40 ° C., the reaction time becomes longer, and if it exceeds 130 ° C., the condensation reaction between methoxysilyl sites, which is a side reaction, tends to proceed, both of which are not preferable. The total reaction time when the reaction temperature is about 40 to 130 ° C. is about 1 to 7 hours.

  The silica content in the cured residue of the methoxysilyl group-containing silane-modified polyimide siloxane resin (see below for the meaning of the cured residue) is preferably 1% or more and less than 15%. When the silica content is less than 1%, the effect of the present invention is not easily obtained. When the silica content is 15% or more, the coating layer shrinks during curing, and the metal foil laminate is slightly warped. Tend to occur.

  The reaction is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves both the resin (A) and the epoxy group-containing methoxysilane partial condensate (B). As such an organic solvent, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide and the like can be used. Moreover, you may use poor solvents, such as xylene and toluene, with respect to these good solvents in the range which is 30 weight% or less of the whole solvent in the range which does not precipitate the said resin (A) and component (b2).

  The method of adding and using the solvent in the reaction system is not particularly limited, but usually the solvent added when synthesizing (1) resin (A) is used as it is. (2) The solvent added when the epoxy group-containing methoxysilane partial condensate (B) is synthesized from the component (b1) and the component (b2) is used as it is. (3) It is added before the reaction between the resin (A) and the epoxy group-containing methoxysilane partial condensate (B). At least one of the three modes may be selected and adopted.

  Moreover, the catalyst for promoting reaction can be used for reaction of resin (A) and an epoxy-group-containing methoxysilane partial condensate (B). For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, benzimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc. Organic phosphines; tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate It can be mentioned tetraphenyl boron salts such over bets like. The catalyst is preferably used at a ratio of about 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyimidesiloxane resin (A).

  The methoxysilyl group-containing silane-modified polyimidesiloxane resin composition of the present invention contains the methoxysilyl group-containing silane-modified polyimidesiloxane resin obtained as described above as an essential component, and the silane-modified polyimidesiloxane resin Has in its molecule a methoxysilyl group derived from the epoxy group-containing methoxysilane partial condensate (B). The methoxysilyl group forms a cured product condensed with each other by sol-gel reaction or demethanol condensation reaction by evaporation of a solvent, heat treatment, or reaction with moisture (humidity). Such a cured product has fine gelled silica sites (high-order network structure of siloxane bonds). In addition, the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition of the present invention can further contain a filler, thereby improving the dimensional stability of the cured film.

  The methoxysilyl group-containing silane-modified polyimide siloxane resin composition of the present invention is characterized by containing the methoxysilyl group-containing silane-modified polyimide siloxane resin as described above, but does not depart from the object of the present invention. In the range, a conventionally known polyimide siloxane resin, the component (b2), an epoxy group-containing methoxysilane partial condensate (B) and the like may be appropriately blended as desired.

  It is appropriate that the resin composition is usually in a liquid state with a curing residue of about 10 to 70% by weight. Moreover, as the solvent, for example, a solvent used in the ring-opening esterification reaction or a polar solvent such as ester, ketone, alcohol, or phenol can be used. In addition, a solvent having poor solubility in a resin composition such as xylene or toluene can be used in combination with the solvent.

  The resin composition may contain at least one polar solvent of N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide. Resin (A) and epoxy group-containing methoxysilane partial condensate (B The total amount of the polar solvent used in the production of () is preferably about 30% by weight or more in each composition. When the content is less than 30%, the resin composition has a high viscosity at room temperature, so that the handleability tends to deteriorate.

  Further, the content of the methoxysilyl group-containing silane-modified polyimidesiloxane resin in the resin composition is not particularly limited, but it is usually preferably 50% by weight or more in the cured residue of the composition. Here, the curing residue means a solid content obtained by applying the above resin composition, followed by sol-gel curing or imidization to remove volatile components, and after applying the resin composition at 100 μm or less. , A solid after being dried and cured at 200 ° C. for 3 hours.

  When there is a large difference in the linear expansion coefficient between the cured film obtained from the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition and the metal foil, the metal foil laminate may be warped. Therefore, it is preferable to add a conventionally known filler to the resin composition so that the linear expansion coefficient approaches that of the metal foil. Fillers include oxides such as carbon, 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, Although titanates such as barium titanate and potassium titanate, phosphates such as tricalcium phosphate, dicalcium phosphate, and primary calcium phosphate can be used, but not limited thereto. Absent. Among these fillers, it is most preferable to use silica in consideration of the stability of the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition, the dispersibility of the filler, and the effect of suppressing warpage. Usually, the filler preferably has an average particle diameter in the range of about 0.01 μm to 5 μm. Fillers less than 0.01 μm are expensive and poor in versatility, and those exceeding 5 μm cannot be dispersed and tend to settle. Moreover, since the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition is excellent in filler dispersibility, the blending amount of the filler is not particularly limited, but the filler weight ratio in the cured film may be 60% or less. preferable. If it exceeds 60%, the flexibility of the cured film tends to be lost. There is no particular limitation on the method of adding the filler as long as it is a stage until film formation using the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition. For example, the polymerization stage of resin (A), epoxy You may add by reaction with a group containing alkoxysilane partial condensate (B), and may add at the time of film forming.

  In addition, the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition has an organic solvent, a plasticizer, a weathering agent, an antioxidant, and a thermal stability, as long as the effects of the present invention are not impaired. Agents, lubricants, antistatic agents, brighteners, colorants, conductive agent release agents, surface treatment agents, viscosity modifiers, coupling agents and the like may be blended.

A desired metal foil laminate is obtained by applying the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition of the present invention to a metal foil, followed by drying by heating and curing. The cured film in the metal foil laminate has a silica (SiO ₂ ) site derived from a methoxysilyl group or filler (in the case of silica) of a methoxysilyl group-containing silane-modified polyimidesiloxane resin.

  Further, the cured film obtained from the methoxysilyl group-containing silane-modified polyimide siloxane resin composition has low water absorption and high insulation properties due to the effect of silica complexation, but the metal foil laminate is particularly used for FPC, TAB, and COF. In this case, it is preferable to adjust so that the dielectric constant at 1 kHz is about 3.5 or less and the water absorption is less than 2%. If the dielectric constant is larger than 3.5, the cured film is too thick to obtain sufficient insulation, and if the water absorption is 2% or more, the dimensional stability is deteriorated or the metal foil laminate is obtained. May be warped.

  Examples of the metal foil used for the metal foil laminate include electrolytic copper foil, rolled copper foil, aluminum foil, and stainless steel foil. Among these, electrolytic copper foil and rolled copper foil are preferable because of their excellent conductivity, heat resistance, mechanical strength, and surface smoothness. Generally, for FPC and TAB, surface-treated copper foil with an increased surface roughness of the adhesive surface of the copper foil is used for the purpose of obtaining adhesiveness with an adhesive, but a methoxysilyl group-containing silane-modified polyamideimide resin is used. The cast film obtained from the composition has very good adhesion to the metal foil without the use of an adhesive, and there is no need for roughening the surface. Untreated copper foil, fine pitch, high frequency Adequate adhesion can be obtained even with a corresponding low-roughness metal foil. Therefore, as the metal foil, it is preferable to use a copper foil having a surface roughness that is not so large, particularly a metal foil laminate having a surface roughness (Rz) of 7 μm or less, particularly Rz of 2.2 μm or less. The thickness of the metal foil is not particularly limited, but is preferably 70 μm or less, particularly preferably 20 μm or less, for use in a fine pitch substrate.

  When drying and curing the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition of the present invention on a metal foil, it is usually carried out in two or more stages in order to suppress foaming due to rapid scattering of volatile components such as solvents. preferable. Accordingly, the curing temperature and heating time are determined in consideration of the amount of methanol by-produced during the sol-gel reaction of the methoxysilyl group-containing silane-modified polyimidesiloxane used, the type of solvent, the thickness of the cured film, and the like. Determine as appropriate. The first stage is preferably performed at 80 to 150 ° C. for 3 to 30 minutes mainly for the purpose of drying the solvent. Subsequently, it is heated at 130 ° C. to 230 ° C., preferably 150 ° C. or higher and lower than 200 ° C. for 1 to 40 minutes to completely remove the residual solvent and complete the sol-gel curing.

  In addition, the adhesion strength of the metal foil / cured film in the metal foil laminate obtained by applying a methoxysilyl group-containing silane-modified polyimidesiloxane resin composition to which a filler has been added onto a metal foil, and drying and curing the resin It may decrease depending on the type and amount of filler constituting the composition. In such a case, after a resin composition not containing a filler is applied onto a metal foil, dried and cured, after forming a cured film having a high coefficient of linear expansion but excellent adhesion to the metal foil Furthermore, by applying a resin composition containing a filler capable of forming a cured film having a lower linear expansion coefficient or a conventionally known polyimide resin having a linear expansion coefficient of 30 ppm or less, drying, and curing, the above disadvantages are eliminated. it can. At this time, the thickness of the cured film formed from the methoxysilyl group-containing silane-modified polyimidesiloxane resin composition is preferably 10 μm or less in order to suppress warpage of the metal foil laminate.

  In addition, the thickness of these insulating layers may be appropriately determined according to the application, but when used for FPC and TAB, the thickness of the cured film excluding the metal foil is about 3 to 100 μm, particularly 5 to 5 μm. It is preferably 50 μm.

  In a metal foil laminate in which a metal foil is bonded to one side, a double-sided metal foil laminate can be obtained by plating the methoxysilyl group-containing silane-modified polyimidesiloxane resin layer side. As the metal plating method, a known method such as an electroless plating method, a combined method of an electroless plating method and an electrolytic plating method, a pulse plating method, a thermal melting method, a plasma method, a sputtering method, or the like can be adopted. In view of the properties, the electroless plating method and the combined use of electroless plating and electrolytic plating are particularly preferable. The electroless plating method is a method in which a metal to be a catalyst is deposited on the surface and inner wall of a base material, and then copper or the like is deposited by an electroless plating method and plated. Moreover, the combined method of electroless plating and electrolytic plating is a method in which electroless plating is thinly deposited, and then a metal is thickened by electrolytic plating and plated. In the present invention, the plating metal is not particularly limited, and examples thereof include copper, nickel, gold, silver, platinum, tin, lead, cobalt, tungsten, molybdenum, palladium, and alloys thereof. Of these, copper is particularly preferred. Various circuit boards can be produced by applying a resist to the metal laminate of the present invention obtained as described above, exposing the resist to etching, and etching the resist.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. In each case,% is based on weight in principle.

Production Example 1 (Production of polyimide siloxane resin (A))
3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride (trade name “BPDA”, manufactured by Mitsubishi Chemical Corporation) in a reactor equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction pipe 20 g, α, ω-bis (3-hydroxypropyl) polydimethylsiloxane (Dow Corning Asia Co., Ltd., trade name “DK X8-8579-4”) 14.09 g, pyridine 10.75 g, N, N-dimethyl 110 g of acetamide and 20 g of toluene were charged and subjected to ring-opening esterification at 120 ° C. for 2 hours. Next, the mixture was cooled to 60 ° C., and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name “Licacid DSDA”) 19.39 g, N, N-dimethyl 70 g of acetamide and 40 g of toluene were added. After further cooling to room temperature, 1.05 g of 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd., trade name “DPE / ODA”), bis [4- (4-aminophenoxy) phenyl] sulfone (Wakayama) Seisei Co., Ltd., trade name “BAPS” (43.19 g) was added in small portions so that the temperature was kept at 40 ° C. or lower, and the mixture was stirred at room temperature for 30 minutes after the addition. Thereafter, the generated water was recovered from the water separator at 170 ° C. for 3 hours while performing dehydration ring-closing reaction to obtain a polyimidesiloxane resin solution (A1) soluble in an organic solvent. The resin had a weight average molecular weight (styrene conversion value by GPC measurement) of 25,000. The imide ring closure rate by NMR and IR analysis was 100%. In addition, the composition ratio of the dihydroxysiloxane (a2) in the polyimidesiloxane resin (A) is 15%. Further, [number of moles of tetracarboxylic dianhydride (a1)] / [number of moles of dihydroxysiloxane (a2) + number of moles of diamines (a3)] = 1.04.

Production Example 2 (Production of polyimide siloxane resin (A))
In the same reactor as in Production Example 1, 20 g of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, 9.44 g of the above “DK X8-8579-4”, 10.75 g of pyridine, N, N— 110 g of dimethylacetamide and 20 g of toluene were charged, and a ring-opening esterification reaction was performed at 120 ° C. for 2 hours. Then, the mixture was cooled to 60 ° C., and 21.03 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride, 70 g of N, N-dimethylacetamide, and 40 g of toluene were added. After further cooling to room temperature, 1.14 g of 4,4′-diaminodiphenyl ether and 46.83 g of bis [4- (4-aminophenoxy) phenyl] sulfone were added little by little so that the temperature was kept below 40 ° C. After the addition, the mixture was continuously stirred at room temperature for 30 minutes. Thereafter, the generated water was recovered from the water separator at 170 ° C. for 3 hours, and a dehydration ring-closing reaction was performed to obtain a polyimidesiloxane resin solution (A2) soluble in an organic solvent. The resin had a weight average molecular weight (styrene conversion value by GPC measurement) of 34,000. The imide ring closure rate by NMR and IR analysis was 100%. In addition, the composition ratio of the dihydroxysiloxane (a2) in the polyimidesiloxane resin (A) is 10%. Further, [number of moles of tetracarboxylic dianhydride (a1)] / [number of moles of dihydroxysiloxane (a2) + number of moles of diamines (a3)] = 1.04.

Production Example 3 (Production of polyimide siloxane resin (A))
In the same reactor as in Production Example 1, 20 g of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, α, ω-bis [3- (4-hydroxyphenyl) propyl] polydimethylsiloxane (Shin-Etsu Chemical) 9.41 g (trade name “X-22-1906”, manufactured by Kogyo Co., Ltd.), 10.75 g of pyridine, 120 g of N, N-dimethylacetamide, and 20 g of toluene were charged and subjected to ring-opening esterification reaction at 120 ° C. for 2 hours. It was. Next, the mixture was cooled to 60 ° C., and 20.96 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride, 48 g of N, N-dimethylacetamide, and 36 g of toluene were added. After further cooling to room temperature, 1.14 g of 4,4′-diaminodiphenyl ether and 46.67 g of bis [4- (4-aminophenoxy) phenyl] sulfone were added little by little so that the temperature was kept below 40 ° C. After the addition, the mixture was continuously stirred at room temperature for 30 minutes. Thereafter, the generated water was recovered from the water separator at 170 ° C. for 3 hours while performing dehydration ring-closing reaction to obtain a polyimidesiloxane resin solution (A3) soluble in an organic solvent. The resin had a weight average molecular weight (styrene conversion value by GPC measurement) of 34,000. The imide ring closure rate by NMR and IR analysis was 100%. In addition, the composition ratio of the dihydroxysiloxane (a2) in the polyimidesiloxane resin (A) is 15%. Further, [number of moles of tetracarboxylic dianhydride (a1)] / [number of moles of dihydroxysiloxane (a2) + number of moles of diamine (a3)] = 1.03.

Production Example 4 (Production of epoxy group-containing methoxysilane partial condensate (B))
In the same reactor as in Production Example 1, 1400 g of glycidol (manufactured by NOF Corporation, trade name “Epiol OH”) and tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 51”, The average number of Si was 4) 8957.9 g, and the mixture was heated to 90 ° C. with stirring in a nitrogen stream. Then, 2.0 g of dibutyltin dilaurate was added as a catalyst and reacted. During the reaction, the produced methanol was distilled off using a water separator, and when the amount reached about 630 g, it was cooled. It took 5 hours to cool after raising the temperature. Subsequently, about 80 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 methoxysilane partial condensate (B1) was obtained. In addition, (equivalent of methoxy group of methoxysilane partial condensate) / (equivalent of hydroxyl group of epoxy alcohol) at the time of preparation = 1 / 0.1.

Production Example 5 (Production of epoxy group-containing methoxysilane partial condensate (B))
The glycidol in Production Example 4 was changed to 2716 g of epoxy alcohol (trade name “EOA” manufactured by Kuraray Co., Ltd.), and the same reaction was performed to obtain an epoxy group-containing methoxysilane partial condensate (B2). In addition, (equivalent of methoxy group of methoxysilane partial condensate) / (equivalent of hydroxyl group of epoxy alcohol) at the time of preparation = 1 / 0.1.

Example 1 (Production of methoxysilyl group-containing silane-modified polyimidesiloxane resin)
In the same reactor as in Production Example 1, 121.58 g of the polyimidesiloxane resin solution (A1) obtained in Production Example 1 and 3.12 g of the epoxy group-containing alkoxysilane partial condensate (B1) obtained in Production Example 4 were charged. After raising the temperature to 90 ° C., the reaction was performed for 3 hours to obtain the desired methoxysilyl group-containing silane-modified polyimidesiloxane resin solution. The resin solution has a cured residue of 30.6%, and the silica content in the cured residue is 4%.

Example 2 (Production of methoxysilyl group-containing silane-modified polyimidesiloxane resin)
In a reactor similar to Production Example 1, 120.69 g of the polyimidesiloxane resin solution (A2) obtained in Production Example 2 and 3.06 g of the epoxy group-containing alkoxysilane partial condensate (B1) obtained in Production Example 4 were charged. After raising the temperature to 90 ° C., the reaction was performed for 3 hours to obtain the desired methoxysilyl group-containing silane-modified polyimidesiloxane resin solution. The resin solution has a cured residue of 30.1%, and the silica content in the cured residue is 4%.

Example 3 (Production of methoxysilyl group-containing silane-modified polyimidesiloxane resin)
In the same reactor as in Production Example 1, 120.69 g of the polyimidesiloxane resin solution (A3) obtained in Production Example 3 and 3.06 g of the epoxy group-containing alkoxysilane partial condensate (B2) obtained in Production Example 5 were charged. After raising the temperature to 90 ° C., the reaction was performed for 3 hours to obtain the desired methoxysilyl group-containing silane-modified polyimidesiloxane resin solution. The resin solution has a cured residue of 30.6%, and the silica content in the cured residue is 4%.

Examples 4 to 6 (Production of methoxysilyl group-containing silane-modified polyimidesiloxane resin composition)
The methoxysilyl group-containing silane-modified polyimidesiloxane resin solutions [(A1) to (A3)] obtained in Examples 1 to 3 were each diluted with N, N-dimethylacetamide to obtain a curing residue of 30.0%. A silane-modified polyimidesiloxane resin composition was obtained.

Example 7 (Production of methoxysilyl group-containing silane-modified polyimidesiloxane resin composition)
9.16 g of the methoxysilyl group-containing silane-modified polyimidesiloxane resin solution obtained in Example 1 was added to a silica filler dispersion [silica filler (made by Tokuyama Co., Ltd., trade name “Leoloseal DM-30S”, average particle diameter of the filler] 10 nm)] obtained by dispersing 1.40 g in 6.36 g of N, N-dimethylacetamide], 30.0% in the cured residue, and 20% silica filler content in the cured residue A methoxysilyl group-containing silane-modified polyimidesiloxane resin composition was obtained.

Comparative Examples 1 and 2 (Comparative Polyimide Siloxane Resin Composition)
The polyimidesiloxane resin solutions (A1) and (A2) obtained in Production Example 1 and Production Example 2 were used as the resin compositions of Comparative Example 1 and Comparative Example 2, respectively.

Comparative Example 3 (Production of Comparative Polyimide Resin Composition Soluble in Organic Solvent)
In the same reaction apparatus as in Production Example 1, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic anhydride 44.32 g, bis [4- (4-aminophenoxy) phenyl] sulfone 1.00 g, N, N-dimethylacetamide (158.41 g) and toluene (39.60 g) were charged and suspended. Subsequently, 0.94 g of 4,4′-diaminodiphenyl ether, 44.61 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Co., Ltd., trade name “BAPP”), N, N-dimethylacetamide (158.41 g) and toluene (39.60 g) were added in small portions so that the temperature was kept at 40 ° C. or lower, and the mixture was stirred at room temperature for 30 minutes after completion of the addition (tetracarboxylic acid relative to the number of moles of amino groups). The number of moles of anhydride groups is 1.07). Thereafter, a dehydration ring-closing reaction was carried out at 170 ° C. for 4 hours while collecting the produced water from a water separator to obtain a comparative polyimide resin solution soluble in an organic solvent. The resin had a weight average molecular weight (styrene conversion value by GPC measurement) of 36,000. The imide ring closure rate by NMR and IR analysis was 100%.

Examples 8-11 and Comparative Examples 4-6 (Preparation of cured film)
The methoxysilyl group-containing silane-modified polyimidesiloxane resin composition obtained in Examples 4 to 7 and the resin composition obtained in Comparative Examples 1 to 3 were each coated on a glass plate with an applicator (wet 200 μm), Each coated glass plate is placed in a dryer, dried and cured stepwise under conditions of 120 ° C. for 10 minutes and then at 200 ° C. for 60 minutes, and then allowed to cool to room temperature, resulting in a film thickness of 25 μm. Each cured film was obtained. Note that the methoxysilyl group-containing silane-modified polyimidesiloxane resin solution obtained in Example 1 provides a cured film with low flexibility when a cured film is prepared under the same conditions. A cured film having a film thickness of 25 μm was obtained in the same manner except that it was 60 minutes at 200 ° C. and 60 minutes at 150 ° C.

For the cured films obtained in Examples 8 to 11 and Comparative Examples 4 to 6, the siloxane-derived portions, silica (SiO ₂ ), and filler content as the constituent components are shown in Table 1.

(Linear expansion coefficient and glass transition point)
The cured film (4 mm × 20 mm) obtained above was subjected to a linear expansion coefficient from 40 ° C. to 200 ° C. and glass using a thermomechanical analyzer (trade name “TMA120C” manufactured by Seiko Instruments Inc.). The transition point was measured. The results are shown in Table 2.

(Water absorption rate)
Measurement weight after leaving the cured film (50 mm × 50 mm) obtained above in a constant temperature bath kept at 50 ° C. for 24 hours, and measurement after immersing in a constant temperature water bath kept at 23 ° C. for 24 hours. The water absorption was calculated from the difference from the weight. The results are shown in Table 2.

(Dielectric constant)
The dielectric constant of the cured film (50 mm × 50 mm) obtained above was measured at a frequency of 1 kHz and a temperature of 23 ° C. using a dielectric constant / dielectric loss tangent measuring instrument (Kitahama Seisakusho Co., Ltd.). The results are shown in Table 2.

  As apparent from Table 2, the linear expansion coefficient could be reduced in the cured film of Example 11 containing the silica filler. The silica hybrid of Example 8 had a high glass transition temperature and improved heat resistance. By increasing the siloxane content and further making a silica hybrid, the water absorption rate could be reduced (in Examples 8 to 10). The dielectric constant could be reduced by increasing the siloxane content and further by using a silica hybrid (Examples 8 to 10). Moreover, the thermal expansion coefficient was able to be reduced greatly by containing a silica filler (the thing of Example 11).

Examples 12 to 13 and Comparative Examples 7 to 9 (Formation of metal foil laminate)
The resin solutions obtained in Examples 8 to 9 and Comparative Examples 4 to 6 were used as electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd., trade name “F2-WS”, film thickness 18 μm, surface roughness Rz = 2. 1) was coated with an applicator (wet 150 μm), placed in a drier, and cured at 120 ° C. for 10 minutes and then at 170 ° C. for 15 minutes to obtain a metal foil laminate having a cured film thickness of 25 μm.

Example 14 (Production of metal foil laminate)
The resin solution obtained in Example 8 was coated on the same electrolytic copper foil as used in Example 13 with an applicator (wet 100 μm), placed in a drier, dried at 120 ° C. for 10 minutes, and then in Example 11. The obtained resin solution is overcoated with an applicator (wet 50 μm), placed in a drier again, and cured under conditions of 120 ° C. for 10 minutes and then 170 ° C. for 15 minutes, thereby a metal foil laminate having a cured film thickness of 25 μm. Got.

(Adhesion)
The delamination strength of each metal foil laminate obtained above was measured according to the standard of JIS C6481. The results are shown in Table 3.

(warp)
The smoothness of the metal foil laminate obtained above was evaluated visually. The evaluation results are shown in Table 3.
◯: There is no warping.
Δ: Slight warping is observed.
X: Warp is obvious.

  As is clear from Table 3, in the metal foil laminates of Comparative Examples 7 and 8 using a high siloxane content but not a silica hybrid (Comparative Examples 4 and 5), the flexibility of the insulating film is low, While the peel strength was not sufficient, in Examples 12 to 14, the interlayer peel strength was 0.8 kg / cm, indicating high adhesion to the copper foil.

Claims (14)

A polyimide siloxane resin soluble in an organic solvent obtained by reacting tetracarboxylic dianhydride (a1), dihydroxysiloxane (a2), and diamines (a3), having a carboxyl group and / or an acid at the molecular end Demethanol reaction of an anhydride group having a carboxyl group in the side chain and the imide ring closure rate of 90% or more (A), epoxy alcohol (b1) and methoxysilane partial condensate (b2) A process for producing a methoxysilyl group-containing silane-modified polyimidesiloxane resin, which comprises subjecting the epoxy group-containing methoxysilane partial condensate (B) obtained by a ring-opening esterification reaction. Dihydroxysiloxane (a2) is represented by the general formula (1):

(Wherein R ¹ independently represents a methylene group or phenylene group having 2 to 6 carbon atoms, R ² independently represents an alkyl group or phenyl group having 1 to 4 carbon atoms, and the number of repeating units n is 3) The production method according to claim 1, which is represented by: The production method according to claim 1 or 2, wherein the composition ratio of the dihydroxysiloxane (a2) in the polyimidesiloxane resin (A) is 1% or more and less than 70%. Each use ratio of tetracarboxylic dianhydride (a1), dihydroxysiloxane (a2), and diamines (a3) in the polyimidesiloxane resin (A) is [mole number of (a1)] / [mole of (a2). The manufacturing method according to any one of claims 1 to 3, which satisfies a condition of number + (number of moles of (a3)] = 1.0 to 1.2. The production method according to any one of claims 1 to 4, wherein the methoxysilane partial condensate (b2) has an average number of Si atoms of 2 to 100 per molecule. Epoxy alcohol (b1) is represented by the general formula (2):

(Wherein m represents an integer of 1 to 10), and the production method according to any one of claims 1 to 5. The method according to any one of claims 1 to 6, wherein the methoxysilyl group-containing silane-modified polyimidesiloxane resin has a silica content of 1% or more and less than 30% in the cured residue. A methoxysilyl group-containing silane-modified polyimidesiloxane resin obtained by the production method according to claim 1. A methoxysilyl group-containing silane-modified polyimidesiloxane resin composition comprising the methoxysilyl group-containing silane-modified polyimidesiloxane resin according to claim 8 and a polar solvent. The methoxysilyl group-containing silane-modified polyimidesiloxane resin composition according to claim 9, which contains a filler as an additional component. The methoxysilyl group-containing silane-modified polyimidesiloxane resin composition according to claim 10, wherein the filler is silica. A cured film obtained by curing the methoxysilyl group-containing silane-modified polyimidesiloxane resin according to claim 8 or the resin composition according to any one of claims 9 to 11. A metal foil laminate obtained by coating the resin composition according to any one of claims 1 to 11 on a metal foil and then heat-curing the resin composition. The metal foil laminate according to claim 13, wherein the heating temperature is 230 ° C or lower.