JP5119757B2 - Polyimide resin composition - Google Patents

Description

  The present invention relates to a resin composition from which a coating film, an adhesive layer, a wiring interlayer insulating film, a flexible circuit board film and the like excellent in toughness and heat resistance can be obtained, a molded product of the composition containing the resin composition, and the resin The present invention relates to a method for treating a molded product obtained using a composition containing the composition, a paint containing the resin composition, and a method for forming a coating film using the paint.

  Heat resistance of a cured product of a resin composition used in the electric and electronic industries such as a heat resistant coating material, an electrical insulating material, for example, an interlayer insulating material of a printed wiring board, a build-up material, a semiconductor insulating material, a heat resistant adhesive, In addition to electrical characteristics such as low dielectric constant and low dielectric loss tangent and flexibility, there is a demand for improvement in storage stability of the resin composition before curing. In particular, in electronic devices such as computers, transmission characteristics such as signal transmission delay of a printed circuit board and occurrence of crosstalk become a problem as the signal speed and frequency increase. Moreover, about the resin composition used for a printed circuit board, the material with the low dielectric constant of the hardened | cured material obtained is calculated | required.

  As a resin composition from which a cured product having excellent heat resistance is obtained, for example, a resin composition containing an epoxy resin is often used. Examples of the resin composition include an epoxy resin having a weight average molecular weight of less than 35,000, a polyfunctional phenol resin, a high molecular weight epoxy resin having a weight average molecular weight of 35,000 or more, a curing accelerator, a reducing agent, and a urea compound. An epoxy resin composition is disclosed (for example, see Patent Document 1). However, even a cured product obtained using the epoxy resin composition is not satisfactory in heat resistance.

  As other resin compositions, for example, many resin compositions containing a polyimide resin are also used. As the resin composition, for example, a thermosetting polyimide resin composition containing a polyimide resin having a carboxyl group and a linear hydrocarbon structure having a number average molecular weight of 300 to 6,000 and an epoxy resin is known. (For example, refer to Patent Document 2). However, even the cured product of the thermosetting polyimide resin composition described in Patent Document 2 does not have sufficient heat resistance.

JP-A-5-295090 JP 2003-292575 A

  The present invention relates to a resin composition from which a coating film, an adhesive layer, a wiring interlayer insulating film, a flexible circuit board film and the like excellent in toughness and heat resistance can be obtained, a molded product of the composition containing the resin composition, and the resin It is providing the processing method of the molding obtained using the composition containing a composition, the coating material containing this resin composition, and the formation method of the coating film using this coating material.

As a result of intensive studies, the present inventor has found the following knowledge.
(1) A resin composition containing a structural residue of a phenol-based compound, a urethane resin formed by a reaction of a phenolic hydroxyl group and an isocyanate group, and an epoxy resin is molded with excellent heat resistance A thing is obtained.

  (2) By adding a condensate of an alkyl alkoxysilane to the molded product, it is possible to impart toughness to the molded product while maintaining heat resistance.

(3) In order to obtain a molded product having heat resistance and toughness, a composition containing a condensate of the polyimide resin and alkylalkoxysilane may be used, or the polyimide resin and alkylalkoxysilane are contained. The composition may be used, and the alkylalkoxysilane may be condensed at the time of molding and / or after molding by means such as heating to obtain a condensate.
The present invention has been completed based on the above findings.

  That is, the present invention provides a polyimide resin (B) having a structure represented by the following general formula (1) and / or the following general formula (2) and a condensate of alkylalkoxysilane and / or alkylalkoxysilane (B). And an organic solvent (C).

（式中、Ｘは１分子中に２個以上のフェノール性水酸基を有するフェノール系化合物から２個のフェノール性水酸基を除いた残基を示す。）

(In the formula, X represents a residue obtained by removing two phenolic hydroxyl groups from a phenolic compound having two or more phenolic hydroxyl groups in one molecule.)

  The present invention also provides a molded article obtained by molding a composition containing the resin composition.

  Moreover, this invention provides the processing method of the molded object characterized by heating at 100-300 degreeC, after making the composition containing the said resin composition into a molded object.

  Moreover, this invention provides the coating material characterized by containing the said resin composition.

  Furthermore, this invention provides the formation method of the coating film characterized by heating at 100-300 degreeC, after apply | coating the said coating material on a base material.

  The resin composition of the present invention can provide a molded product having a sufficient breaking strength while having the heat resistance of the polyimide skeleton. Moreover, the molded product which has heat resistance, and also has sufficient breaking strength is easily obtained by the processing method of the molded product of this invention. Moreover, the coating material of the present invention can provide a coating film having heat resistance and further sufficient breaking strength. Furthermore, the coating film of the present invention can easily obtain a coating film having heat resistance and further sufficient breaking strength by the coating film forming method of the present invention.

  The polyimide resin (A) in the thermosetting polyimide resin composition used in the present invention is an isocyanate group and a phenolic hydroxyl group as a urethane bond as represented by the general formula (1) and / or the general formula (2). And have a connected structure. As the polyimide resin (A), a polyimide resin that dissolves in an organic solvent is particularly preferable because it is easy to handle.

  Examples of the polyimide resin having the structure represented by the general formula (1) include a polyimide resin having a structure represented by the following general formula (3).

（上記式中Ｒｘ^１およびＲｘ^２は同一でも異なっていても良く、ポリイソシアネート化合物から二つのイソシアネート基を除いた残基を示す。Ｘは１分子中に２個以上のフェノール性水酸基を有するフェノール系化合物から２個のフェノール性水酸基を除いた残基を示す。）

(In the above formula, Rx ¹ and Rx ² may be the same or different and represent a residue obtained by removing two isocyanate groups from a polyisocyanate compound. X is a phenol having two or more phenolic hydroxyl groups in one molecule. (A residue obtained by removing two phenolic hydroxyl groups from a series compound.)

  Moreover, as a polyimide resin which has a structure represented by the said General formula (2), the polyimide resin etc. which have a structure represented by following General formula (4) are mentioned, for example.

（上記式中Ｒｘ^１はポリイソシアネート化合物から二つのイソシアネート基を除いた残基を示す。Ｘは１分子中に２個以上のフェノール性水酸基を有するフェノール系化合物から２個のフェノール性水酸基を除いた残基を示す。）

(In the above formula, Rx ¹ represents a residue obtained by removing two isocyanate groups from a polyisocyanate compound. X represents removing two phenolic hydroxyl groups from a phenolic compound having two or more phenolic hydroxyl groups in one molecule. The remaining residues are shown.)

Rx ¹ and Rx ² in the general formula (3) and the general formula (4) may be the same or different.

Here, in the general formula (3), when Rx ¹ and / or Rx ² correspond to R ⁵ of the general formula (15) described later, the general formula (15) was bonded to the general formula (1). It becomes a branched polyimide resin. When Rx ¹ in the general formula (4) corresponds to R ⁵ in the general formula (15), the general formula in formula (15) (2) had a structure bound branched polyimide resin.

  Examples of X in the general formulas (1) to (4) include the following structures.

（式中Ｒ^１は、単結合あるいは２価の連結基であり、Ｒ^２は同一でも異なっていても良く、水素原子または炭素原子数１〜１８のアルキル基を示す。）

(Wherein R ¹ is a single bond or a divalent linking group, and R ² may be the same or different, and represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

（式中Ｒ^１は、直接結合あるいは２価の連結基であり、Ｒ^２は同一でも異なっていても良く、水素原子または炭素原子数１〜１８のアルキル基を示す。ａとｂとｃとの合計は１以上である。）

(In the formula, R ¹ is a direct bond or a divalent linking group, and R ² may be the same or different, and represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. A, b and c; The sum of is 1 or more.)

（式中Ｒ^３は、水素原子または炭素原子数１〜１８のアルキル基または下記一般式（８）で示される構造を示す。）

(In the formula, R ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a structure represented by the following general formula (8).)

  The polyimide resin (A) used in the present invention is at least one selected from the group consisting of the general formulas (5), (6), (7) and (9) as X in the general formulas (1) and (2). The polyimide resin having the following structure is preferable because a curable polyimide resin composition is obtained from which a cured product having excellent heat resistance is obtained, and among them, the structures represented by the general formulas (5) and (6) are more preferable. . In particular, the polyimide resin (A) used in the present invention has a structure that imparts flexibility to the cured product as described later. For example, in the case of a polyimide resin having a structure such as the general formula (13) described later, the general formula ( As X in 1) and general formula (2), the structure represented by general formula (6) is preferable.

As R ¹ in the structure represented by the general formula (5) or the general formula (6), for example, a direct bond; a carbonyl group, a sulfonyl group, a methylene group, an isopropylidene group, a hexafluoroisopropylidene group, an oxo group, And divalent linking groups such as a dimethylsilylene group, a fluorene-9-diyl group, and a tricyclo [5.2.1.02,8] decane-diyl group. Examples of R ² include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, and stearyl group. And an alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group having 1 to 18 carbon atoms as R ³ in the structure represented by the general formula (7) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, stearyl group and the like.

  In the present invention, the carbonyl group is the following structural formula (1a), the sulfonyl group is the following structural formula (1b), the methylene group is the following structural formula (1c), the isopropylidene group is the following structural formula (1d), and hexafluoroisopropylidene. The redene group has the following structural formula (1e), the oxo group has the following structural formula (1f), the dimethylsilylene group has the following structural formula (1g), the fluorene-9-diyl group has the following structural formula (1h), and tricyclo [5.2. The 1.02,8] decane-diyl group is represented by the following structural formula (1i). These are residues such as biphenol, tetramethylbiphenol, bisphenol A, bisphenol F, bisphenol S, naphthalenediol, and dicyclopentadiene modified bisphenol. (In the figure, * represents a binding site.) In addition, two hydroxyl groups are excluded from polyphenol compounds such as phenol novolac resin, cresol novolac resin, polyphenol resin synthesized from naphthol, alkylphenol and formaldehyde condensate. It may be a structural residue.

Among R ¹ represented by the general formula (5) and the general formula (6), a structure represented by a direct bond, the general formula (1b), the general formula (1c), and the general formula (1d) is provided. A thermosetting polyimide resin composition excellent in solubility and compatibility is obtained, and it is also preferable because synthesis when obtaining the polyimide resin (A) is easy. Of the R ² , a hydrogen atom and a methyl group are preferable. Moreover, among R ^{1 in} the general formula (6), the structure represented by the general formula (1i) is preferable because a thermosetting polyimide resin composition having excellent heat resistance can be obtained. The structure represented by the general formula (1i) is represented as the following general formula (11).

  The polyimide resin (A) used in the present invention may have a structure represented by the general formula (1) and / or a structure represented by the general formula (2), and above all, the general formula (1) And a polyimide resin having a structure represented by the general formula (2) is preferable because a thermosetting polyimide resin composition having good curability can be obtained. Here, X in the structure represented by the general formula (1) and the structure represented by the general formula (2) may be the same or different.

  As a polyimide resin which has a structure represented by the said General formula (6), the polyimide resin which has the following structures is mentioned, for example.

R ¹ may be the same or different and is the same as described above. Rx ¹ represents a residue obtained by removing two isocyanate groups from a polyisocyanate compound. R ⁹ represents a residue structure obtained by removing an acid anhydride group from a tetracarboxylic acid anhydride. Each of s and t is an integer of 1 to 10, and each unit of s and t enclosed is randomly connected. 1) When s is 1, the polyphenol structure is present at the end corresponding to the general formula (2). 2) When s is 2, the molecular main chain corresponding to the general formula (1) The polyphenol structure is present and 3) When s is 3 or more, the structure of the polyimide resin is branched. Furthermore, the form in which s is 1, 2, and 3 or more may be present in the molecule at the same time.

  In the general formula (6-2), as a typical structure when s is 1, for example, a structure represented by the following general formula (6-3) can be exemplified.

In General Formula (6-3), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. R ⁷ is a hydrogen atom or a structure represented by the following general formula (6-4), and R ⁸ is a structure represented by the general formula (6-4). u is an integer of 1 to 100.

（式中Ｒ^１は、直接結合あるいは２価の連結基であり、Ｒ^２は同一でも異なっていても良く、水素原子または炭素原子数１〜１８のアルキル基を示す。ｖは０〜８の整数である。

(In the formula, R ¹ is a direct bond or a divalent linking group, R ² may be the same or different, and represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. V is 0-8. It is an integer.

  In the general formula (6-2), as a typical structure when s is 2, for example, a structure represented by the following general formula (6-5) can be exemplified.

In the general formula (6-5), Rx ¹ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are the same as described above. R ¹⁰ has a structure represented by the following general formula (6-6).

In the general formula (6-6), R ¹ and R ² are the same as described above. W is an integer of 0-8.

  In the general formulas (6-2), (6-3), (6-4), (6-5), and (6-6), when tetracarboxylic dianhydride is used at the time of polyimide resin synthesis , The portion showing an imide bond has a structure represented by the following general formula (6-7). When tricarboxylic acid anhydride is used, the following general formula (6-8) or general formula (6- 9). The structures represented by general formula (6-7), general formula (6-8), and general formula (6-9) may be used alone or in combination.

R ⁹ represents a residue structure obtained by removing an acid anhydride group from a tetracarboxylic acid anhydride. R ¹¹ represents a residue structure obtained by removing an acid anhydride group and a carboxyl group from a tricarboxylic acid anhydride.

  Specific examples of the polyimide resin having the structure represented by the general formula (1) and the structure represented by the general formula (2) as the polyimide resin (A) include, for example, the following general formula (12-1). The polyimide resin etc. which have the structure represented can be mentioned.

一般式（１２−１）においてＸは上記と同じである。Ｒｘ^３はポリイソシアネート化合物から２つのイソシアネート基を除いた残基を示す。一般式（１２−１）中のＡは一般式（１）、一般式（６−７）、一般式（６−８）及び（６−９）で示される構造からなる群から選ばれる構造であるが、全て一般式（１）であることはない。また、ｎは１〜１００である。

In general formula (12-1), X is the same as above. Rx ³ represents a residue obtained by removing two isocyanate groups from a polyisocyanate compound. A in general formula (12-1) is a structure selected from the group consisting of the structures represented by general formula (1), general formula (6-7), general formula (6-8) and (6-9). Although there is no general formula (1). N is 1 to 100.

In the polyimide resin having the structure represented by the general formula (3) and the general formula (4), when Rx ¹ and Rx ² are residues obtained by removing two isocyanate groups from a bifunctional diisocyanate compound, A polyimide resin having a linear structure as represented by the formula (12) is obtained. In addition, when Rx ¹ and Rx ² have a structure that is a residue obtained by removing two isocyanate groups from a trifunctional or higher polyfunctional isocyanate compound, a polyimide resin having a branched structure is obtained.

  Among the polyimide resins (A), the polyimide resin having the structure represented by the general formula (2) has a phenolic hydroxyl group at the terminal and can be cured by reacting with the epoxy resin (B) described later. It is. A cured product of a general phenol compound and an epoxy resin has limitations in terms of glass transition temperature (Tg), heat resistance, dielectric properties, mechanical properties, linear expansion, etc., but is represented by the general formula (2). Since the polyimide resin having the structure has an imide structure in the resin skeleton, it is possible to obtain a cured product having high performance that cannot be obtained by conventional techniques.

  The polyimide resin (A) used in the present invention may have a structure represented by the general formula (1) and / or the general formula (2), and above all, a structure represented by the general formula (1). And a polyimide resin having a structure represented by the general formula (2) is more preferable because a cured product having excellent curability and heat resistance can be obtained.

  As the polyimide resin (A) used in the present invention, the polyimide resin branched in the structure represented by the following general formula (15) has improved compatibility with other resin components, improved solvent solubility, and obtained curing. It is preferable because the heat resistance of the coating film is good.

（式中Ｒ^５はジイソシアネート化合物からイソシアネート基を除いた残基構造を示す。）

(In the formula, R ⁵ represents a residue structure obtained by removing an isocyanate group from a diisocyanate compound.)

Examples of R ⁵ in the general formula (15) include an aromatic residue structure, an aliphatic residue structure, and an alicyclic residue structure. Among these, those having 4 to 13 carbon atoms can be preferably used. The structure of R ⁵ is preferably a combination of two or more structures from the viewpoint of preventing crystallization and improving solubility. In particular, the combined use of an aromatic residue structure and an aliphatic or alicyclic residue structure is preferred.

  The polyimide resin branched in the structure represented by the general formula (15) can be obtained, for example, by synthesis using an isocyanurate type polyisocyanate compound as a raw material.

  The polyimide resin (A) used in the present invention is preferably a polyimide resin having an imide bond represented by the following general formula (16), the following general formula (17-1), or the following general formula (17-2).

R ⁹ in the general formula (16) represents a residue structure obtained by removing an acid anhydride group from a tetracarboxylic acid anhydride. R ¹¹ in the general formulas (17-1) and (17-2) represents a residue structure obtained by removing the acid anhydride group and the carboxyl group from the tricarboxylic acid anhydride.

As described above, R ⁹ is a residue obtained by removing the acid anhydride group of the tetracarboxylic acid anhydride. Examples of such a structure include the following structures.

As described above, R ¹¹ is a residue structure obtained by removing an acid anhydride group and a carboxyl group from a tricarboxylic acid anhydride. Examples of such a structure include the following structures.

  Among the polyimide resins (A), examples of the polyimide resin having a structure represented by the general formula (16) include a polyimide resin having a structure represented by the following general formula (18).

（上記式中Ｒｘ^１およびＲｘ^２は同一でも異なっていても良く、ポリイソシアネート化合物から二つのイソシアネート基を除いた残基を示す。Ｒ^６はテトラカルボン酸無水物から酸無水物基を除いた残基構造を示す。）

(In the above formula, Rx ¹ and Rx ² may be the same or different and represent a residue obtained by removing two isocyanate groups from a polyisocyanate compound. R ⁶ is obtained by removing an acid anhydride group from a tetracarboxylic acid anhydride. The residue structure is shown.)

In the general formula (18), when Rx ¹ and / or Rx ² corresponds to R ⁵ in the general formula (15), a branched polyimide resin having a structure in which the general formula (18) is bonded to the general formula (15). It becomes.

  Examples of the polyimide resin having the structure represented by the general formula (17-1) include a polyimide resin having a structure represented by the following general formula (19-1) and general formula (19-2). It is done.

（式中Ｒｘ^１、Ｒｘ^２及びＲ^１１は上記と同じである。）

(Wherein Rx ¹ , Rx ² and R ¹¹ are the same as above)

In the general formula (19-1) and general formula (19-2), when Rx ¹ and / or Rx ² corresponds to R ⁵ in the general formula (15), the general formula (19) is represented in the general formula (15). A branched polyimide resin having a bonded structure is obtained.

  As the polyimide resin (A) used in the present invention, the polyimide resin branched in the structure represented by the general formula (15) has improved compatibility with other resin components, improved solvent solubility, and obtained curing. It is preferable because the heat resistance of the coating film is good.

  The polyimide resin (A) used in the present invention is produced, for example, by a production method in which a polyphenol compound (a1) having two or more phenolic hydroxyl groups, a polyisocyanate compound (a2), and an acid anhydride (a4) are reacted. Can be easily obtained.

  Examples of the polyphenol compound (a1) having two or more phenolic hydroxyl groups include hydroquinone, biphenol, tetramethylbiphenol, ethylidene bisphenol, bisphenol A, bisphenol F, bisphenol S, cyclohexylidene bisphenol (bisphenol Z), and dimethyl. Butylidenebisphenol, 4,4 ′-(1-methylethylidene) bis [2,6-dimethylphenol], 4,4 ′-(1-phenylethylidene) bisphenol, 5,5 ′-(1-methylethylidene) bis [1,1′-biphenyl-2-ol], naphthalenediol, dicyclopentadiene-modified bisphenol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and hydroquinone Response product, and the like.

  As the polyphenol compound (a1), a trifunctional or higher functional phenol compound such as a novolak resin of an alkylphenol such as a phenol novolak resin, a cresol novolak resin, and a nonylphenol novolak resin can also be used.

  As the polyphenol compound (a1), it is preferable to use a polyphenol compound containing two phenolic hydroxyl groups, that is, a bifunctional polyphenol compound. Among these, bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S are more preferable.

  Moreover, since the hardened | cured material excellent in a flame retardance and heat resistance is obtained, when obtaining a polyimide resin (A), naphthalene diol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 It is preferred to use a reaction product of oxide and hydroquinone.

  In addition, you may use together monofunctional phenolic compounds, such as a phenol and a cresol, in the range which does not impair the effect of this invention.

  Further, as a polyphenol compound other than the polyphenol compound containing two phenolic hydroxyl groups, a polyphenol compound having three or more functional groups, for example, an alkylphenol novolak such as phenol novolak, cresol novolak, nonylphenol novolak, sylock type polyphenol resin, or the like can be used. Furthermore, monofunctional phenolic compounds such as phenol and cresol can be used as long as the effects of the present invention are not impaired.

  As a polyisocyanate compound (a2) used by this invention, an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, etc. can be used, for example.

  Examples of the aromatic polyisocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4. '-Diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,3-bis Aromatic diisocyanates such as (α, α-dimethyl isocyanate methyl) benzene, tetramethylxylylene diisocyanate, diphenylene ether-4,4′-diisocyanate, and naphthalene diisocyanate Over preparative compounds.

  Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylenemethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, and norbornylene diisocyanate. .

  As the polyisocyanate compound (a2), an isocyanate prepolymer obtained by reacting the polyisocyanate compound (a2) and various polyol components in advance with an excess of isocyanate groups can be used or used in combination.

  The polyimide resin (A) used in the thermosetting polyimide resin composition of the present invention is more preferable because it has a branched structure, thereby improving compatibility with other resin components such as solvent solubility and a curing agent. As the branching method, as the polyisocyanate compound (a2), for example, a tri- or higher functional polyisocyanate compound having an isocyanurate ring, which is an isocyanurate body such as the diisocyanate compound, or such polyisocyanate compound and the diisocyanate is used. Preference is given to using mixtures with compounds.

  The trifunctional or higher functional polyisocyanate compound having an isocyanurate ring is formed by, for example, converting one or two or more diisocyanate compounds into an isocyanurate in the presence or absence of an isocyanuration catalyst such as a quaternary ammonium salt. And those made of a mixture of isocyanurates such as trimer, pentamer, and heptamer. Specific examples of the isocyanurate form of the polyisocyanate compound include isophorone diisocyanate isocyanurate type polyisocyanate, hexamethylene diisocyanate isocyanurate type polyisocyanate, hydrogenated xylene diisocyanate isocyanurate type polyisocyanate, norbornane diisocyanate isocyanurate type. Aliphatic polyisocyanates such as polyisocyanate, isocyanurate type polyisocyanate of diphenylmethane diisocyanate, isocyanurate type polyisocyanate of tolylene diisocyanate, isocyanurate type polyisocyanate of xylene diisocyanate, isocyanurate type polyisocyanate of naphthalene diisocyanate, etc. It is done.

  When the polyisocyanate compound (a2) is used in combination with a diisocyanate compound and a trifunctional or higher functional diisocyanate compound having an isocyanurate ring, the aromatic diisocyanate as the diisocyanate compound and the trifunctional or higher functional diisocyanate compound having the isocyanurate ring are used. It is preferable to use a mixture containing an isocyanurate type polyisocyanate of an aliphatic diisocyanate and / or an isocyaninate type polyisocyanate of an alicyclic diisocyanate.

  When an aliphatic diisocyanate compound is used as the polyisocyanate compound (a2), a thermosetting polyimide resin composition having excellent solubility can be obtained, and a cured coating film having good electrical properties can be obtained.

  Furthermore, the polyisocyanate compound (a2) is used in combination with a polyisocyanate compound other than the above, for example, the diisocyanate compound, a buret body, an adduct body, an allohanate body of the diisocyanate, or a polymethylene polyphenyl polyisocyanate (crude MDI). May be.

  The polyisocyanate compound (a2) used in the present invention is preferably used in combination of two or more polyisocyanate compounds since a thermosetting polyimide resin composition having good solvent solubility can be obtained. In addition, since the cured coating film excellent in heat resistance is obtained, it is preferable to use the isocyanurate body in combination. When using an isocyanurate body together, it is preferable to set it to 70 weight% or less of the amount of all the polyisocyanate compounds (a2) in the sense of preventing the high molecular weight and gelation of the resin.

  Examples of the acid anhydride (a4) include an acid anhydride having one acid anhydride group and an acid anhydride having two acid anhydride groups. Examples of the acid anhydride having one acid anhydride group include aromatic tricarboxylic acid anhydrides such as trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride.

  Examples of the acid anhydride having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3'. , 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl -2,2 ', 3,3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride , Naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3 5,6,7-Hexahydronaphthalene- , 2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,3,9,10-tetracarboxylic dianhydride , Berylene-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1 , 1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) ) Propane dianhydride, 2 1,3-bis (3,4-carboxyphenyl) propane dianhydride, bis (3,4-carboxyphenyl) sulfone dianhydride, bis (3,4-carboxyphenyl) ether dianhydride,

Ethylene glycol bisanhydro trimellitate, propylene glycol bis anhydro trimellitate, butanediol bis anhydro trimellitate, hexamethylene glycol bis anhydro trimellitate, polyethylene glycol bis anhydro trimellitate, polypropylene lenglycol bis Anhydro trimellitate, other alkylene glycol bisan hydroxy trimellitate, etc. are mentioned.

  Among the acid anhydrides (a4), pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3', 4,4'-tetra Carboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-2,2', 3,3'-tetracarboxylic dianhydride, and ethylene glycol bisanhydro Trimellitate is preferred.

  As the acid anhydride (a4), one or more of these can be used. Further, an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid monoacid anhydride may be mixed with an aromatic tetracarboxylic acid dianhydride.

  As explained above, the polyimide resin (A) used in the resin composition of the present invention comprises a polyphenol compound (a1) having two or more phenolic hydroxyl groups, a polyisocyanate compound (a2), an acid anhydride ( It can be obtained by a production method in which a4) is reacted.

  In the method for producing the polyimide resin, the polyphenol compound (a1) and the acid anhydride (a4) react with the polyisocyanate compound (a2). In order to leave the terminal as a phenolic hydroxyl group, the total number of moles of the phenolic hydroxyl group in the polyphenol compound (a1) and the acid anhydride group in the acid anhydride (a4) is the polyisocyanate compound. It is preferable to make it react on the conditions which become larger than the number of moles of the isocyanate group in (a2). In terms of synthesis stability and various performances of the cured product, [{number of moles of phenolic hydroxyl group in (a1) + number of moles of acid anhydride group in (a4)} / isocyanate group in (a2) The number of moles] is preferably in the range of 1 to 10, more preferably in the range of 1.1 to 7. Further, (a1) and (a4) are preferably present in an amount of 5% or more, and more preferably 10% or more, based on the total weight of the polyphenol compound (a1) and the acid anhydride (a4). More preferably.

  The polyimide resin (A) used in the present invention may be produced by a single-stage reaction or by a reaction having two or more stages.

  In the case of producing in a one-stage reaction, for example, a raw material such as a polyphenol compound (a1), a polyisocyanate compound (a2) and an acid anhydride (a4) is charged in a reaction vessel, and the temperature is raised while stirring. The reaction is allowed to proceed while decarboxylating.

  When the production is carried out by a reaction having two or more reaction steps, for example, an acid anhydride (a4) is charged in the presence of the polyisocyanate compound (a2), and an isocyanate group and a polyphenol compound (a1) remaining during or after the reaction. ) Can be produced by reacting with a phenolic hydroxyl group. The reaction can also be carried out by charging the polyphenol compound (a1) and the polyisocyanate compound (a2) and charging the acid anhydride (a4) during or after the reaction.

  Furthermore, the acid anhydride (a4) may be charged in the presence of the polyphenol compound (a1), and the isocyanate group remaining during or after the reaction may react with the acid anhydride (a4).

  The reaction temperature can be in the range of 50 ° C. to 250 ° C., and is preferably performed at a temperature of 70 ° C. to 180 ° C. in terms of reaction rate and prevention of side reactions.

  In the method for producing a polyimide resin used in the present invention, the polyphenol compound (a1) having two or more phenolic hydroxyl groups, the polyisocyanate compound (a2), and the acid anhydride (a4) are converted into (a1), (a2 ) And (a4) are preferably used so as to be 5 to 50% by weight, 20 to 70% by weight, and 20 to 70% by weight, respectively.

  The reaction is preferable because the stability of the resulting polyimide resin is improved when the reaction is performed until almost all isocyanate groups have reacted. Moreover, you may make it react by adding an alcohol and a phenol compound with respect to the isocyanate group which remains a little.

  In the method for producing the polyimide resin (A) used in the present invention, it is preferable to use an organic solvent because a uniform reaction can proceed. Here, the organic solvent may be present after being present in the system in advance or may be introduced in the middle. In order to maintain an appropriate reaction rate, the proportion of the organic solvent in the system is preferably 80% by weight or less of the reaction system, and more preferably 10 to 70% by weight. As such an organic solvent, since a compound containing an isocyanate group is used as a raw material component, an aprotic polar organic solvent having no active proton such as a hydroxyl group or an amino group is preferable.

  As the aprotic polar organic solvent, for example, polar organic solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and γ-butyrolactone can be used. In addition to the above solvents, ether solvents, ester solvents, ketone solvents, petroleum solvents and the like may be used as long as they are soluble. Various solvents may be mixed and used.

  Examples of the ether solvent include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl. Polyethylene glycol dialkyl ethers such as ether and triethylene glycol dibutyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate; Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, polyethylene glycol monoalkyl ether acetates such as triethylene glycol monobutyl ether acetate;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol Polypropylene glycol dialkyl ethers such as propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; Polypropylene glycol monoalkyl ether acetate such as triglycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate Dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of copolymerized polyether glycols; Examples include ether glycol monoalkyl esters and monoalkyl ethers. It is.

  Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the ketone solvent include acetone, methyl ethyl ketone, and cyclohexanone. In addition, as the petroleum solvent, it is also possible to use toluene, xylene, other high-boiling aromatic solvents, and aliphatic and alicyclic solvents such as hexane and cyclohexane.

  The ratio of the organic solvent in the system when the organic solvent is used when producing the polyimide resin (A) used in the present invention is preferably 80% by weight or less of the reaction system, and preferably 10 to 70% by weight. More preferred.

  The weight average molecular weight of the polyimide resin (A) used in the present invention is from 800 to 800 because a thermosetting polyimide resin composition having good solvent solubility is obtained and a cured coating film having various physical properties is obtained. 50,000 is preferable, and 1,000 to 20,000 is more preferable.

  As for the phenolic hydroxyl group equivalent of the polyimide resin (A) used by this invention, 400-10,000 are preferable.

In addition, the measurement of the weight average molecular weight of resin, such as a polyimide resin (A) used by this invention, was calculated | required by polystyrene conversion on the following conditions using the gel permeation chromatograph.
Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: Guard column SUPER HZ-H manufactured by Tosoh Corporation
+ 4 TSKgel SUPER HZm-m manufactured by Tosoh Corporation Detector; RI (differential refractometer)
Data processing: GPC-8020 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 0.35ml / min
Standard: Polystyrene sample: 0.2% by weight tetrahydrofuran solution in terms of resin solids filtered through a microfilter (100 ml)

  In addition, it uses as a thermosetting resin composition by using the thermoplastic polyimide resin containing a hydroxyl group like the polyimide resin (A) used by the resin composition of this invention, and also containing an epoxy resin (D). can do.

  The epoxy resin (D) preferably has two or more epoxy groups in the molecule. Examples of such epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, and bisphenol F type epoxy resin; novolak types such as phenol novolac epoxy resin, cresol novolac type epoxy resin, and bisphenol type novolak. Epoxy resins; epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; biphenyl type epoxy resins such as epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol; Epoxy resin having naphthalene skeleton; aromatic epoxy resin such as epoxy resin having fluorene skeleton and hydrogenated product of these aromatic epoxy resins; neopentyl glycol diglycidyl Aliphatic epoxy resins such as ether and 1,6-hexanediol diglycidyl ether; fats such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate Cyclic epoxy resins; and heterocyclic ring-containing epoxy resins such as triglycidyl isocyanurate. Among these, an aromatic epoxy resin is preferable because a thermosetting polyimide resin composition excellent in opportunity physical properties of a cured coating film is obtained, and a novolac type epoxy resin is more preferable. Even if epoxy resin (D) is contained, it is thermoplastic.

  The blending amount of the polyimide resin (A) and the epoxy resin (D) can be used in a ratio of (A1) / (D) of 1/100 to 50/1 as a weight ratio of the resin, and more preferably. Is from 1/10 to 20/1.

  A compound that reacts with the phenolic hydroxyl group of the polyimide resin (A) can be further added to the resin composition of the present invention. Specific examples include epoxy compounds other than the epoxy resin (D), isocyanate compounds, silicates, and alkoxysilane compounds.

  Examples of the isocyanate compound include aromatic isocyanate compounds, aliphatic isocyanate compounds, and alicyclic isocyanate compounds. Preferably, a polyisocyanate compound having two or more isocyanate groups in one molecule is preferable. A blocked isocyanate compound can also be used.

  Examples of the alkylalkoxysilane that is one of the components (B) used in the present invention include alkyltrialkoxysilane and dialkyldialkoxysilane.

  Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, Examples thereof include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, and phenyltributoxysilane.

  Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, and diphenyldimethoxy. Silane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldipropoxysilane, methylethyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane , Methylphenyldipropoxysilane, methylphenyldibutoxysilane, trimethylmethoxysilane, trimethyl ether Kishishiran, triethyl silane, triethyl silane, triphenyl methoxy silane, triphenyl ethoxy silane, and the like.

  Examples of the condensate of alkylalkoxysilane which is one of the components (B) used in the present invention include the above-mentioned condensates of alkyltrialkoxysilanes and condensates of dialkyldialkoxysilanes.

  When using the alkylalkoxysilane used in the present invention, other alkoxysilanes such as tetraalkoxysilane can be used in combination as long as the effects of the present invention are not impaired. Moreover, the condensate of the alkyl alkoxysilane used by this invention is good also as a condensate by using together other alkoxysilanes, for example, tetraalkoxysilane etc., in the range which does not impair the effect of this invention.

  Among the alkylalkoxysilanes that are one of the components (B), methyltrimethoxysilane and / or dimethyldimethoxysilane have excellent compatibility with the polyimide resin (A), and a tough molded product or cured coating film. Since it is obtained, it is preferable. Among the condensates of alkyl alkoxysilanes that are one of the components (B), condensates containing methyltrimethoxysilane and / or dimethyldimethoxysilane as essential components are excellent in compatibility with the polyimide resin (A), And since a tough molded article and a cured coating film are obtained, it is preferable. ,

  Moreover, as a condensate of alkyl alkoxysilane, a condensate having a molecular weight of 500 to 100,000 is preferable, and a condensate having a molecular weight of 1000 to 50,000 is more preferable.

  The amount of the alkylalkoxysilane condensate and / or the alkylalkoxysilane (B) used is strong, and it is possible to obtain a molded product and a cured coating film that are less susceptible to cracking. On the other hand, 1-100 weight part is preferable, 1-50 weight part is more preferable, and 5-30 weight part is still more preferable.

  Examples of the organic solvent (C) used in the present invention include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetates such as carbitol acetate, cellosolve, Examples thereof include carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and γ-butyrolactone. As the organic solvent (C), γ-butyrolactone is preferable, but when the polyimide resin having the structure represented by the general formula (13) is used as the polyimide resin (A), acetates are preferable, and acetates The combined use of aromatic hydrocarbons is more preferable.

  The composition of the present invention comprises a polyimide resin (A) having a structure represented by the following general formula (1) and / or the following general formula (2) and a condensate of alkylalkoxysilane and / or alkylalkoxysilane (B). And an organic solvent (C). Furthermore, the resin composition of the present invention includes polyester resins, phenoxy resins, PPS resins, PPE resins, polyarylene resins and other binder resins, phenol resins, melamine resins, alkoxysilane curing agents, polybasic acid anhydrides, cyanate compounds, and the like. Curing agents such as curing agents or reactive compounds, melamine, dicyandiamide, guanamine and derivatives thereof, imidazoles, amines, phenols having one hydroxyl group, organic phosphines, phosphonium salts, quaternary ammonium salts, photocationic catalysts, etc. It is also possible to add a curing accelerator, a filler, and other additives.

  Further, as the curing accelerator, a urethanization catalyst is preferably used in combination. Examples of such a urethanization catalyst include 1,8-diazabicyclo [5,4,0] undecene-7 (hereinafter DBU) and its organic salt compounds, dialkyltin alkyls such as triethylenediamine, dibutyltin diacetate, and dibutyltin dilaurate. Examples thereof include esters and carboxylates of bismuth.

  Moreover, the resin composition of this invention can add a various filler, an organic pigment, an inorganic pigment, an extender, a rust preventive agent, etc. further as needed. These may be used alone or in combination of two or more.

  Examples of the filler include barium sulfate, barium titanate, silicon oxide powder, fine particulate silicon oxide, silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like. It is done.

  Examples of the organic pigment include azo pigments; copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and quinacridone pigments.

  Examples of the inorganic pigment include chromates such as chrome lead, zinc chromate and molybdate orange; ferrocyanides such as bitumen, titanium oxide, zinc white, bengara, iron oxide; metal oxides such as chromium carbide green, Cadmium yellow, cadmium red; metal sulfides such as mercury sulfide; selenides; sulfates such as lead sulfate; silicates such as ultramarine; carbonates, cobalt biored; phosphates such as manganese purple; aluminum powder, zinc dust Metal powders such as brass powder, magnesium powder, iron powder, copper powder and nickel powder; carbon black and the like.

  In addition, any of other coloring, rust prevention, and extender pigments can be used. These may be used alone or in combination of two or more.

  The resin composition of the present invention contains an organic solvent (C). Usually, after forming a molded product such as an interlayer insulating material for a printed circuit board using the resin composition of the present invention, the organic solvent (C) is removed by leaving it under heating (for example, 50 to 300 ° C.). By this operation, when alkyl alkoxysilane is used as (B) in the resin composition, it becomes a condensate by hydrolysis condensation in the presence of water. The water required for the hydrolytic condensation may not be added to the composition of the present invention when it is covered with atmospheric water, but may be added as necessary. In order to promote hydrolysis, a catalyst such as an acid or a base may be added, but a weakly basic catalyst is particularly preferred from the viewpoint of hydrolyzability and the pot life of the solution.

  Even when an alkylalkoxysilane condensate is used as (B) in the resin composition, if this condensate has an alkoxy group, hydrolysis condensation may occur, but the effect of the present invention is not affected. In addition, when the organic solvent (C) is removed after the molding is prepared, it is preferable to use a condensate of alkylalkoxysilane as (B) when not performed under heating.

  The molded product of the present invention is formed by molding the resin composition of the present invention. The molded product of the present invention can be particularly suitably used as an insulating layer for printed circuit boards.

  The processing method of the molded article of the present invention is characterized in that a composition containing the resin composition of the present invention is made into a molded article and then heated at 50 to 300 ° C. By performing the heating step in this way, even when an alkylalkoxysilane that is not condensed is used as the resin composition of the present invention, it becomes a condensate and a tough molded product. The heating temperature is preferably 100 to 250 ° C.

  The paint of the present invention is characterized by containing the resin composition of the present invention. Moreover, the coating-film formation method of this invention is characterized by heating at 50-300 degreeC, after apply | coating the coating material of this invention on a base material. Even when an alkylalkoxysilane which is not condensed is used as the resin composition by heating after applying the paint, it becomes a condensate and a tough coating film. The heating temperature is preferably 100 to 250 ° C.

  The substrate used in the method for forming the coating film can be used without any particular limitation. Examples of the substrate include plastic, metal, and wood.

  In addition, the resin composition of the present invention may be in the form of a film (adhesive film) comprising a resin composition layer (A layer) and a support film (B layer), which is a suitable form for production of a flexible circuit board. Can be used.

  The adhesive film is prepared according to various methods, for example, by preparing a resin varnish obtained by dissolving the resin composition of the present invention in an organic solvent, applying the resin varnish to a support film, and applying the organic solvent by heating or hot air blowing. It can manufacture by making it dry and forming a resin composition layer.

  The support film (B layer) serves as a support when the adhesive film is produced, and is finally peeled off or removed in the production of the flexible circuit board. Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, and release paper and copper foil. The metal foil etc. can be mentioned. In addition, when using copper foil as a support body film, it can remove by etching with etching liquid, such as ferric chloride and cupric chloride. The support film may be subjected to a release treatment in addition to a mat treatment and a corona treatment, but it is more preferable that the release treatment is performed in consideration of releasability. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers.

  Organic solvents for preparing the varnish include, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl Examples thereof include carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition is usually 5% by mass or less, preferably 3% by mass or less. The specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the varnish. It can be dried to some extent. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

  The thickness of the resin composition layer (A layer) can usually be in the range of 5 to 500 μm. The preferred range of the thickness of the A layer varies depending on the use of the adhesive film, and when used for manufacturing a multilayer flexible circuit board by the build-up method, the thickness of the conductor layer forming the circuit is usually 5 to 70 μm. The thickness of the A layer corresponding to the layer is preferably in the range of 10 to 100 μm.

  The A layer may be protected with a protective film. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The protective film is peeled off during lamination. As the protective film, the same material as the support film can be used. Although the thickness of a protective film is not specifically limited, Preferably it is the range of 1-40 micrometers.

  Especially the adhesive film of this invention can be used conveniently for manufacture of a multilayer flexible circuit board. Below, the method to manufacture a multilayer flexible circuit board is demonstrated. The adhesive film of the present invention can be suitably laminated on a flexible circuit board with a vacuum laminator. The flexible circuit board used here is mainly composed of a conductive layer (circuit) patterned on one or both sides of a substrate such as a polyester substrate, a polyimide substrate, a polyamideimide substrate, or a liquid crystal polymer substrate, as well as alternating circuits and insulating layers. It is also possible to use a multilayer flexible circuit board that is layered and has a circuit formed on one or both sides for further multilayering. In addition, from the viewpoint of adhesion of the insulating layer to the circuit board, the surface of the circuit should have been previously roughened with a surface treatment agent such as hydrogen peroxide / sulfuric acid or MEC Etch Bond (MEC Co., Ltd.). preferable.

  Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo Morton, a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Techno Engineering Co., Ltd., Hitachi AIC ( A vacuum laminator manufactured by Co., Ltd. can be mentioned.

In the lamination, when the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the circuit board while being pressurized and heated. The laminating conditions include pre-heating the adhesive film and the circuit board as required, laminating at a pressure of preferably 70 to 140 ° C., a pressure of pressure of preferably 1 to 11 kgf / cm ² and laminating under a reduced pressure of an air pressure of 20 mmHg or less. preferable. The laminating method may be a batch method or a continuous method using a roll.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature and the support film is peeled off. Next, the thermosetting polyimide resin composition laminated on the circuit board is cured by heating. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes. In addition, when a support body film has a peeling process or peeling layers, such as a silicon | silicone, a support body film can also be peeled after heat-hardening of a thermosetting polyimide resin composition, or after heat-hardening and punching.

  After the insulating layer, which is a cured product of the thermosetting polyimide resin composition, is formed, the circuit board is drilled by a method such as drilling, laser, plasma, or a combination thereof to form via holes and through holes as necessary. It may be formed. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, surface treatment of the insulating layer (cured product of the thermosetting polyimide resin composition) is performed. The surface treatment can employ a method used in a desmear process, and can be performed in a form that also serves as a desmear process. As a chemical used in the desmear process, an oxidizing agent is generally used. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, and the like. Preferably, an alkaline permanganate solution (for example, potassium permanganate, sodium hydroxide aqueous solution of sodium permanganate), which is an oxidizer widely used for roughening the insulating layer in the production of multilayer printed wiring boards by the build-up method. It is preferable to carry out the treatment using A treatment with a swelling agent can also be performed before the treatment with the oxidizing agent. Further, after the treatment with an oxidizing agent, neutralization treatment with a reducing agent is usually performed.

  After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The conductor layer can be formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  As a method for forming a circuit by patterning the conductor layer, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. In the case of the subtractive method, the thickness of the electroless copper plating layer is 0.1 to 3 μm, preferably 0.3 to 2 μm. An electroplating layer (panel plating layer) is formed thereon with a thickness of 3 to 35 μm, preferably 5 to 20 μm, an etching resist is formed, and etching is performed with an etching solution such as ferric chloride or cupric chloride. After forming a conductor pattern by this, a circuit board can be obtained by peeling an etching resist. In the case of the semi-additive method, after forming the electroless copper plating layer with an electroless copper plating layer thickness of 0.1 to 3 μm, preferably 0.3 to 2 μm, a pattern resist is formed, and then the electrolytic copper A circuit board can be obtained by peeling after plating.

  A film in which the support film is replaced with a heat-resistant resin layer (heat-resistant resin film), that is, a film comprising a polyimide resin composition layer (A layer) and a heat-resistant resin layer (C layer) is a base film for a flexible circuit board. Can be used as Similarly, a film composed of a resin composition layer (A layer), a heat resistant resin layer (C layer) and a copper foil (D layer) can be used as a base film of a flexible circuit board. In this case, the base film has a layer structure in the order of A layer, C layer, and D layer. In the base film as described above, the heat-resistant resin layer is not peeled off and constitutes a part of the flexible circuit board.

  A film in which an insulating layer (A ′ layer) made of a cured product of the resin composition of the present invention is formed on a heat-resistant resin layer (C layer) can be used as a base film for a single-sided flexible circuit board. Moreover, it consists of the film which has a layer structure of the order of A 'layer, C layer, and A' layer, and A 'layer, C layer, and copper foil (D layer), A' layer, the order of C layer, and D layer Similarly, a film having a layer structure can be used as a base film for a double-sided flexible circuit board.

  Examples of the heat-resistant resin used for the heat-resistant resin layer include a polyimide resin, an aramid resin, a polyamideimide resin, and a liquid crystal polymer. In particular, a polyimide resin and a polyamideimide resin are preferable. Moreover, on the characteristic used for a flexible circuit board, the breaking strength is 100 MPa or more, the breaking elongation is 5% or more, the thermal expansion coefficient between 20 and 150 ° C. is 40 ppm or less, and the glass transition temperature is 200 ° C. or more or the decomposition temperature is 300 ° C. It is preferable to use the above heat resistant resin.

  As the heat-resistant resin satisfying such characteristics, a heat-resistant resin that is commercially available in the form of a film can be suitably used. For example, a polyimide film “Upilex-S” manufactured by Ube Industries, Ltd., Toray DuPont Co., Ltd. ) Polyimide film "Kapton", Kaneka Chemical Co., Ltd. polyimide film "Apical", Teijin Advanced Films Ltd. "Aramika", Kuraray Co., Ltd. liquid crystal polymer film "Bexstar", Sumitomo Bakelite Co., Ltd. A polyether ether ketone film “Sumilite FS-1100C” and the like are known.

  The thickness of the heat-resistant resin layer is usually 2 to 150 μm, preferably 10 to 50 μm. As the heat-resistant resin layer (C layer), a surface-treated layer may be used. Examples of the surface treatment include dry treatment such as mat treatment, corona discharge treatment and plasma treatment, chemical treatment such as solvent treatment, acid treatment and alkali treatment, sand blast treatment and mechanical polishing treatment. In particular, from the viewpoint of adhesion to the A layer, it is preferable that plasma treatment is performed.

  A base film for a single-sided flexible circuit board composed of an insulating layer (A ′) and a heat-resistant resin layer (C) can be produced as follows. First, similarly to the adhesive film described above, a resin varnish prepared by dissolving the resin composition of the present invention in an organic solvent is prepared, this resin varnish is applied on a heat-resistant resin film, and the organic solvent is removed by heating or hot air blowing. It is made to dry and a thermosetting polyimide resin composition layer is formed. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, the resin composition layer is heated and dried to form an insulating layer of the thermosetting polyimide resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  The production of a base film of a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat resistant resin layer (C) layer and a copper foil (D layer) A resin composition may be formed on a copper-clad laminated film made of (D layer) and manufactured in the same manner as described above. Examples of the copper clad laminated film include a cast method two-layer CCL (Copper-clad laminate), a sputtering method two-layer CCL, a laminate method two-layer CCL, and a three-layer CCL. The thickness of the copper foil is preferably 12 μm or 18 μm.

  Commercially available two-layer CCL includes Espanex SC (manufactured by Nippon Steel Chemical Co., Ltd.), Neoprex I <CM>, Neoprex I <LM> (Mitsui Chemicals), S'PERFLEX (Sumitomo Metal Mining Co., Ltd.) Nikaflex F-50VC1 (manufactured by Nikkan Kogyo Co., Ltd.) and the like are mentioned as the commercially available three-layer CCL.

  The production of a base film of a double-sided flexible circuit board film comprising three layers of an insulating layer (A ′ layer), a heat resistant resin layer (C layer) and an insulating layer (A ′ layer) can be carried out as follows. First, in the same manner as the adhesive film described above, a resin varnish prepared by dissolving the resin composition of the present invention in an organic solvent is prepared, this resin varnish is applied on a support film, and the organic solvent is dried by heating or hot air blowing. To form a resin composition layer. Conditions such as the organic solvent and drying conditions are the same as those for the adhesive film. The thickness of the resin composition layer is preferably in the range of 5 to 15 μm.

  Next, this adhesive film is laminated on both surfaces of the heat resistant resin film. Lamination conditions are the same as described above. Moreover, if the resin composition layer is previously provided on one side of the heat-resistant film, the lamination may be only on one side. Next, the resin composition layer is cured by heating to form an insulating layer that is a layer of the resin composition. The conditions for heat curing are usually selected in the range of 150 to 220 ° C. for 20 to 180 minutes, more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes.

  A method for producing a flexible circuit board from the base film for the flexible circuit board will be described. In the case of a base film comprising an A ′ layer, a C layer, and an A ′ layer, first, after heat-curing, a circuit board is drilled by a method such as drilling, laser, or plasma to form a through hole for conduction on both sides. . In the case of a base film composed of an A ′ layer, a C layer, and a D layer, holes are formed by the same method to form via holes. In particular, drilling with a laser such as a carbon dioxide laser or a YAG laser is generally used.

  Next, a surface treatment of the insulating layer (resin composition layer) is performed. About surface treatment, it is the same as that of the case of the adhesive film mentioned above. After the surface treatment, a conductor layer is formed by plating on the surface of the insulating layer. The formation of the conductor layer by plating is the same as in the case of the adhesive film described above. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.

  Next, the conductor layer is patterned to form a circuit to obtain a flexible circuit board. When a base film composed of an A layer, a C layer, and a D layer is used, a circuit is also formed on the copper foil that is the D layer. As a circuit formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. Details are the same as in the case of the adhesive film described above.

  The single-sided or double-sided flexible circuit board obtained in this way can be produced as a multilayer flexible circuit board by using the adhesive film of the present invention, for example, as described above.

  The resin composition of the present invention is also useful as a material for forming a stress relaxation layer between a semiconductor and a substrate substrate. For example, in the same manner as described above, all or part of the uppermost insulating layer of the substrate substrate is formed by the adhesive film obtained by using the resin composition of the present invention, and the resin is connected by connecting the semiconductor. A semiconductor device in which a semiconductor and a substrate substrate are bonded via a cured product of the composition can be manufactured. In this case, the thickness of the resin composition layer of the adhesive film is appropriately selected within a range of 10 to 1000 μm. The resin composition of the present invention can form a conductor layer by plating, and a circuit pattern can also be produced by simply forming a conductor layer by plating on an insulating layer for stress relaxation provided on a substrate substrate. Is possible.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following, all parts and “%” are “% by weight” unless otherwise specified.

Synthesis Example 1 [Production of Polyimide Resin (A)]
A flask equipped with a stirrer, a thermometer and a condenser was charged with 632 g of γ-butyrolactone, 48.0 g (0.25 mol) of trimellitic anhydride, and 102.5 g (0 of TMEG (ethylene glycol bisanhydrotrimellitate)). .25 mol), 17.2 g (0.10 mol) of TDI (tolylene diisocyanate), 100 g (0.42 mol) of MDI (diphenylmethane diisocyanate), 8 g (0.04 mol) of BPF (bisphenol F), The temperature was raised to 120 ° C. while paying attention to heat generation while stirring, dissolved and reacted at this temperature for 1 hour, further heated to 160 ° C. over 1 hour, and then reacted at this temperature for 3 hours. I let you. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown liquid. The resin solid content concentration was adjusted to 20.0% with γ-butyrolactone to obtain a polyimide resin (A-1) solution having a viscosity at 25 ° C. of 20 Pa · s.

  The obtained polyimide resin (A) solution was coated on a KBr plate, and the infrared absorption spectrum of the sample in which the solvent was volatilized was measured. As a result, 2270 cm −1, which is the characteristic absorption of the isocyanate group, disappeared completely, and 725 cm − Characteristic absorption of the imide ring was confirmed at 1, 1780 cm <-1> and 1720 cm <-1>. The amount of carbon dioxide generated was 44.0 g (1.0 mol), which was monitored by the change in the weight charged to the flask. From this, it was concluded that the total amount of 0.50 mol of trimellitic anhydride and TMEG was converted to imide bonds or amide bonds, and the remaining isocyanate groups were linked to the resin by forming urethane bonds with BPF. The

Synthesis example 2 (same as above)
In a flask equipped with a stirrer, a thermometer and a condenser, 200 g of γ-butyrolactone, 36.9 g (0.192 mol) of trimellitic anhydride, and 6.9 g (0.04 mol) of TDI (tolylene diisocyanate) , 40 g (0.16 mol) of MDI (diphenylmethane diisocyanate) and 3.2 g (0.016 mol) of BPF (bisphenol F) were charged, and the temperature was raised to 120 ° C. while paying attention to heat generation while stirring. Then, the mixture was dissolved and reacted for 1 hour, further heated to 160 ° C. over 1 hour, and then reacted at this temperature for 3 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a brown liquid. The resin solid content concentration was adjusted to 25.4% with γ-butyrolactone, and a solution of a polyimide resin (A-2) having a viscosity at 25 ° C. of 90 Pa · s was obtained.

  As a result of coating the obtained polyimide resin (A-2) solution on a KBr plate and measuring the infrared absorption spectrum of the sample in which the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group completely disappeared, Characteristic absorption of the imide ring was confirmed at 725 cm −1, 1780 cm −1 and 1720 cm −1. The amount of carbon dioxide generated was 16.9 g (0.38 mol), which was tracked by the change in the weight charged to the flask. From this, it is concluded that the total amount of 0.192 mol of trimellitic anhydride is converted to an imide bond or an amide bond, and the remaining isocyanate groups are linked to the resin by forming a urethane bond with BPF.

Synthesis Example 3 [Preparation of Comparative Control Polyimide Resin (a)]
In a flask equipped with a stirrer, thermometer and condenser, 4951 g of EDGA and a polyisocyanate having an isocyanurate ring derived from isophorone diisocyanate (isocyanate group content 18.2%, isocyanurate ring-containing triisocyanate content 85% ) 2760 g (12 moles as isocyanate groups) and polytail HA [hydrogenated liquid polybutadiene having hydroxyl groups at both ends, manufactured by Mitsubishi Chemical Corporation, number average molecular weight 2,100, hydroxyl value 51.2 mgKOH / g] 2191 g (hydroxyl groups) 2 mol), and the temperature was raised to 80 ° C. while stirring while paying attention to heat generation. The urethanization reaction was carried out at this temperature for 3 hours. Next, 1536 g of EDGA and 1536 g (8 mol) of TMA (trimellitic anhydride) were further charged, and the temperature was raised to 160 ° C. and reacted for 4 hours to obtain a light brown solution of polyimide resin for comparison (a-1). The resin solid content concentration of the solution of the comparative polyimide resin (a-1) was 55%.

  As a result of coating the obtained polyimide resin for comparison (a-1) on a KBr plate and measuring the infrared absorption spectrum of the sample where the solvent was volatilized, 2270 cm-1 which is the characteristic absorption of the isocyanate group was completely obtained. It disappeared, and imide ring absorption was observed at 725 cm −1, 1780 cm −1 and 1720 cm −1, characteristic absorption of the isocyanurate ring was observed at 1690 cm −1 and 1460 cm −1, and characteristic absorption of the urethane bond was confirmed at 1550 cm −1. The acid value of the polyimide resin is 79 mgKOH / g in terms of solid content, the concentration of the isocyanurate ring is 0.66 mmol / g (in terms of resin solid content), and the number average molecular weight (hereinafter abbreviated as Mn) is 5,900. The weight average molecular weight (hereinafter abbreviated as Mw) was 24,000.

Example 1
The resin composition 1 of the present invention was prepared according to the formulation shown in Table 1. Using the obtained thermosetting polyimide resin composition 1, the compatibility, film-forming property, heat resistance, mechanical properties, electrical properties and dimensional stability were evaluated according to the following methods. The results are shown in Table 3. In addition, all the compounding quantities (weight part) in a table | surface are solid-text equivalent weight.

(1) Evaluation of compatibility The compatibility state when the resin composition 1 was prepared and the state of the coating film after the resin composition 1 after the preparation was coated on a glass plate and dried at 120 ° C. were as follows: Evaluation was based on the evaluation criteria.
Evaluation Criteria A: Uniformity is easily obtained by stirring in the preparation of the resin composition 1, and no foreign matter or the like is observed on the coating surface.
○: In the preparation of the resin composition 1, it becomes uniform by stirring, and no foreign matter or the like is seen on the coating surface.
(Triangle | delta): It is hard to become uniform by stirring in preparation of the resin composition 1, and a foreign material etc. are seen a little on the coating-film surface.
X: In preparation of the resin composition 1, it does not melt | dissolve uniformly but a coating surface can confirm a repelling, a foreign material, and an insoluble matter.

(2) Evaluation of coating film-forming property A test piece obtained by applying resin composition 1 to a tin plate with an applicator so that the film thickness after drying was 30 μm, and then drying at 110 ° C. for 30 minutes was obtained at room temperature. The coating film appearance was evaluated according to the following evaluation criteria.
Evaluation criteria ○: No abnormalities such as cracks are observed in the coating film.
Δ: Some cracks are observed in the coating film.
X: Cracks occurred on the entire surface of the coating film.

(3) Evaluation of heat resistance
<Preparation of test piece>
After coating the resin composition 1 on a glass epoxy substrate laminated with copper stays so that the film thickness after curing is 50 μm, the resin composition 1 is dried for 30 minutes with a dryer at 50 ° C. and for 30 minutes with a dryer at 100 ° C. The mixture was heated with a dryer at 200 ° C. for 60 minutes and cooled to room temperature to prepare a cured coating film.

<Heat resistance test method>
The cured coating film was immersed in a molten solder bath at 260 ° C. for 30 seconds and cooled to room temperature. This solder bath immersion operation was performed three times in total, and the appearance of the cured coating film was evaluated according to the following evaluation criteria.
○: Appearance abnormality is not observed in the coating film.
Δ: Abnormalities such as swelling and peeling are slightly observed in the coating film.
X: Abnormalities such as swelling and peeling are observed on the entire surface of the coating film.

(4) Evaluation of mechanical properties Mechanical properties were evaluated by conducting a tensile test of a coating film (film) and obtaining an elastic modulus, breaking strength, and breaking elongation.
<Preparation of test piece>
It coated on the tinplate board | substrate so that the film thickness of the coating film which can obtain the resin composition 1 might be set to 50 micrometers. Next, this coated plate was dried with a dryer at 50 ° C. for 30 minutes, with a dryer at 100 ° C. for 30 minutes, and with a dryer at 200 ° C. for 60 minutes to form a coating film (film). After cooling to room temperature, the coating film (film) was cut into a predetermined size, isolated from the substrate, and used as a measurement sample.

<Tensile test measurement method>
Five samples for measurement were prepared and subjected to a tensile test under the following conditions to determine the elastic modulus, breaking strength, and breaking elongation. It represents that it is a coating film which is excellent in a softness, so that the value of an elasticity modulus is low. It represents that it is a coating film which is excellent in a softness | flexibility, so that the value of breaking elongation is high. And it shows that it is a tough coating film, so that the value of breaking strength is high.
Measuring instrument: Tensilon manufactured by Toyo Baldwin, Inc. Sample shape: 10 mm x 70 mm
Between chucks: 20 mm
Tensile speed: 10 mm / min
Measurement atmosphere: 22 ° C., 45% RH

Examples 1-3 and Comparative Examples 1-2
The thermosetting polyimide resin compositions 2 to 8 and the comparative thermosetting polyimide resin compositions 1 'to 2' were prepared in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were added. did. Using this, various evaluations were performed in the same manner as in Example 1, and the results are shown in Table 3.

Table footnote N680: Cresol novolac epoxy resin, epoxy equivalent 214 Softening point 81 ° C
EP2050: Solid bisphenol A type epoxy resin, epoxy equivalent 640
2E4MZ: 2-ethyl-4-methyl-imidazole DBTA: dibutyltin acetate SS-101: partial condensate of tetramethoxysilane and methyltrimethoxysilane. 1,000 molecular weight

Claims (14)

Following general formula (1) and the polyimide resin having the structure represented by the following general formula (2) (A), and condensates of alkyl alkoxysilane and / or alkyl alkoxysilane (B), an organic solvent ( A resin composition containing C) ,
Content of the said alkyl alkoxysilane condensate and / or alkyl alkoxysilane (B) is 1-50 weight part with respect to 100 weight part of polyimide resins (A), The resin composition characterized by the above-mentioned.

(In the formula, X represents a residue obtained by removing two phenolic hydroxyl groups from a phenolic compound having two or more phenolic hydroxyl groups in one molecule.) The resin composition according to claim 1, wherein the polyimide resin (A) is a polyimide resin containing a structural unit represented by the following general formula (16) and / or a structure represented by the general formula (17).

(Wherein R ⁹ represents a residue structure obtained by removing an acid anhydride group from a tetracarboxylic acid anhydride, and R ¹¹ represents a residue structure obtained by removing an acid anhydride group and a carboxyl group from a tricarboxylic acid anhydride. ) X is represented by the following general formula (5), the general formula (7) and one or more structure selected from the group consisting of structures represented by the general formula (9) in the general formula (1) and one general formula (2) The resin composition according to claim 1.

Wherein R ¹ is a direct bond , carbonyl group, sulfonyl group, methylene group, isopropylidene group, hexafluoroisopropylidene group, oxo group, dimethylsilylene group, fluorene-9-diyl group or tricyclo [5.2.1.02,8 ] A decane-diyl group , R ² may be the same or different, and represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.)

(Wherein R ³ represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or a structure represented by the following general formula (8).)

Formula (1) and one general formula (2) X is the structure in which claim 1 resin composition according to the general formula (6) in.

Wherein R ¹ is a direct bond , carbonyl group, sulfonyl group, methylene group, isopropylidene group, hexafluoroisopropylidene group, oxo group, dimethylsilylene group, fluorene-9-diyl group or tricyclo [5.2.1.02,8 A decane-diyl group , R ² may be the same or different, and represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and the sum of a, b and c is 1 or more.) The resin composition according to claim 4, wherein R ¹ in the general formula (6) has a structure represented by a methylene group and / or the following general formula (11).

The resin composition according to claim 1, wherein the polyimide resin (A) is a polyimide resin branched in a structure represented by the following general formula (15).

(In the formula, R ⁵ represents a residue structure obtained by removing an isocyanate group from a diisocyanate compound.) 2. The condensate of the alkylalkoxysilane is a condensate obtained by condensing methyltrimethoxysilane and / or dimethyldimethoxysilane, and the alkylalkoxysilane is methyltrimethoxysilane and / or dimethyldimethoxysilane. The resin composition as described. 2. The resin composition according to claim 1, wherein the alkyltrialkoxysilane condensate is a condensate having a molecular weight of 500 to 100,000. Furthermore, the resin composition of Claim 1 containing an epoxy resin (D). A molded product obtained by molding a composition containing the resin composition according to any one of claims 1 to 9 . The molded article according to claim 10, which is an interlayer insulating material for a printed circuit board. After the composition containing the resin composition of any one of claims 1-9 and a molded product, the processing method of the molding, characterized by heating at 50 to 300 ° C.. A paint comprising the resin composition according to any one of claims 1 to 9 . A method for forming a coating film, wherein the coating composition according to claim 13 is applied on a substrate and then heated at 50 to 300 ° C.