KR102422913B1 - Polycarbonate imide resin and resin composition comprising same - Google Patents

Abstract

(1) adhesiveness (2) insulation reliability (3) humidification solder heat resistance (4) solvent solubility, (5) flame retardancy (6) polycarbonate imide resin excellent in brittleness resistance of B-stage adhesive film, and a resin composition comprising the same; and providing an electronic component having a solder resist layer, a surface protection layer, an interlayer insulating layer, or an adhesive layer obtained by curing the resin composition. As a polycarbonate imide resin (A) having a skeleton of a specific structure, when the sum of the amide structure, imide structure, amic acid structure, and urea structure in the polycarbonate imide resin (A) is 100 mol%, the urea structure is Polycarbonate-imide resin (A) whose content is 3 mol% or less.

Description

Polycarbonate imide resin and resin composition comprising same

The present invention relates to a polycarbonate imide resin and an adhesive using the same, and more particularly, to an adhesive having excellent insulation, flexibility, flame retardancy, and fluidity, and suitable for a coverlay film, an adhesive film, a three-layer copper clad laminate, and the like.

Generally, flexible printed wiring boards (hereinafter also referred to as FPCs) are applied to wiring board materials and mounting board materials for electronic devices requiring flexibility and small space properties. For example, it is widely used in device mounting boards for display devices used in liquid crystal display devices, plasma displays, organic EL displays, etc., as well as inter-board relay cables and operation switch boards for smartphones, tablet device terminals, digital cameras, portable game machines, etc. .

In recent years, with the miniaturization, thickness reduction, and high functionality of electronic devices, high integration of electronic circuits is progressing. Accordingly, higher adhesive properties, insulation reliability, heat resistance of humidification solder, and the like are required for FPC coverlays (hereinafter also referred to as CL) and adhesives used between layers.

As a measure for improving the heat resistance of the humidification solder, it is generally considered to lower the polarity of the resin to reduce the water absorption of the resin composition. However, since adhesiveness to a circuit material (copper foil) fell when resin polarity was reduced, there existed a problem that these characteristics coexistence were difficult.

By the way, the adhesive used for FPC apply|coats a liquid resin composition on a release film, and winds up the B-stage adhesive film obtained by volatilizing a solvent in roll form, and, after that, copper foil, polyimide from a release film. Temporarily attached to a circuit material such as a film and used by thermocompression bonding. In general, in the winding process of the B-stage adhesive film, flexibility for not generating cracks in the adhesive film is required, and in the thermocompression bonding process, a small amount of the adhesive outflow from the CL end surface is required.

As a resin used for CL and an interlayer insulating layer, it is excellent in heat resistance, insulation, and chemical-resistance, and solvent-soluble closed cyclic polyimide resin is proposed. However, since a high boiling point solvent such as N-methyl-2-pyrrolidone is generally used as a solvent for a wholly aromatic polyimide-based resin varnish polymerized with only an aromatic monomer, 200 during drying/curing There was a problem in that a curing process at a high temperature of at least °C and a long period of time was required, and thermal deterioration of the electronic component occurred.

In addition, since wholly aromatic polyimide resins generally have a high glass transition temperature, the embedding property when thermocompression bonding an adhesive to a base material such as a polyimide film or copper foil is deteriorated, and the adhesive strength is lowered. there was

On the other hand, polysiloxane-modified polyimide-based resins are disclosed in (Patent Document 1), (Patent Document 2), etc.

Further, for improving the solvent solubility in a low boiling point solvent, for example, (Patent Document 3), etc., a method of copolymerizing an acrylonitrile butadiene having a reactive functional group with a wholly aromatic polyamideimide-based resin excellent in solvent solubility has been proposed. .

Further, for example, (Patent Document 4) or the like, a method of copolymerizing a polycarbonate diol having a reactive functional group with a wholly aromatic polyimide-based resin excellent in solvent solubility has been proposed.

Patent Document 1: Japanese Patent Laid-Open No. 7-304950 Patent Document 2: Japanese Patent Laid-Open No. Hei 8-333455 Patent Document 3: Japanese Patent Laid-Open No. 2003-289594 Patent Document 4: Japanese Patent No. 5748638

However, the polysiloxane-modified polyimide-based resin described in Patent Documents 1 and 2 uses diamine having an expensive dimethylsiloxane structure as a starting material, and is poor in economic efficiency. Moreover, there existed a problem that adhesiveness fell with the increase of polysiloxane copolymerization amount. Moreover, in the polyamideimide resin described in patent document 3, it was necessary to increase the copolymerization amount of acrylonitrile butadiene, and there existed a possibility that insulation reliability could fall as a result. Moreover, since the polyimide precursor solution of patent document 4 has many amic-acid structures, there existed a possibility that the storage stability of a resin solution (it is also mentioned varnish hereafter) might fall.

The present invention has been made in the background of these prior art problems. That is, the object of the present invention is (1) adhesiveness (2) insulation reliability (3) humidification solder heat resistance (4) solvent solubility, (5) flame retardancy (6) polycarbonate imide excellent in brittleness resistance of B-stage adhesive film It is providing the electronic component which has resin, the resin composition containing it, and the soldering resist layer obtained by hardening|curing the said resin composition, a surface protection layer, an interlayer insulating layer, or a contact bonding layer.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject was solvable by the means shown below, and arrived at this invention.

That is, this invention consists of the following structures.

In the polycarbonate imide resin (A) having the structure described in the general formula [I], the sum of the amide structure, imide structure, amic acid structure, and urea structure in the polycarbonate imide resin (A) is 100 mol% Polycarbonate imide resin (A) characterized in that the content of the urea structure is 3 mol% or less.

(In the general formula [I], a plurality of R is each independently a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.)

When all the constituent components of polycarbonate imide resin (A) are 200 mol%, it is preferable to contain 15 mol% or more of the structure of general formula [I].

A resin composition comprising the polycarbonate imide resin (A) and an epoxy resin (B) having two or more epoxy groups per molecule.

It is also preferable to include a phosphorus-based flame retardant (C).

According to the present invention, in addition to (1) adhesiveness (2) insulation reliability (3) humidification solder heat resistance (4) solvent solubility, (5) flame retardancy (6) B-stage adhesive film embrittlement resistance, which was difficult to simultaneously satisfy conventionally An excellent polycarbonate imide resin, a resin composition comprising the same, and an electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer obtained by curing the resin composition can be provided.

Hereinafter, the present invention will be described in detail. The polycarbonate imide resin (A) of the present invention is a resin having a skeleton of a specific structure and a urea structure of a specific amount or less. Moreover, the resin composition of this invention is a composition containing a polycarbonate imide resin (A) and an epoxy resin (B), and containing a phosphorus type flame retardant (C) as needed.

<Polycarbonate imide resin (A)>

The polycarbonate imide resin (A) of this invention is demonstrated. Polycarbonate imide resin (A) is resin which has a structure as described in General formula [I] in skeleton of the said resin. By having the polycarbonate skeleton represented by the general formula [I], the excellent adhesiveness and flexibility of the polycarbonate imide resin (A) can be expressed.

In the general formula [I], a plurality of R each independently represents a divalent organic group having 1 or more carbon atoms. Preferred carbon number is 2 or more, More preferably, it is 4 or more. Moreover, it is preferable that it is 20 or less, More preferably, it is 10 or less, More preferably, it is 8 or less, Especially preferably, it is 6 or less. Specific examples of the divalent organic group having 1 or more carbon atoms are not particularly limited, and aliphatic groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group or octylene group which may have a substituent; Aromatic groups, such as a phenylene group and a biphenylene group, and alicyclic groups, such as a cyclohexylene group, are mentioned. Among these, an aliphatic group is preferable, and n-pentylene group and n-hexylene group are more preferable. Moreover, n is an integer of 1 or more, Preferably it is 2 or more, More preferably, it is 4 or more. An upper limit is not specifically limited, It is preferable that it is 20 or less, More preferably, it is 15 or less. By setting it within the said range, the adhesiveness and flexibility excellent in polycarbonate-imide resin (A) can be expressed.

The polycarbonate skeleton represented by the general formula [I] (hereinafter, in the general formula [I], the weight ratio of the portion excluding the hydroxyl group from the polycarbonate diol is referred to as the polycarbonate diol content rate.) is polycarbonate imide resin (A) When the total constituents of are 200 mol%, it is preferable to contain 15 mol% or more of the structure described in the general formula [I], more preferably 16 mol% or more, and still more preferably 17 mol% or more. . When there are too few, adhesiveness and flexibility may fall. Moreover, it is preferable that it is 90 mol% or less, More preferably, it is 70 mol% or less, More preferably, it is 50 mol% or less. When too large, a flame retardance may fall. Here, the structural component (structural unit) of the polycarbonate imide resin (A) refers to the following (a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a poly represented by the general formula [II] It is set as the acid dianhydride which has carbonate skeleton, (c) an isocyanate compound, and another acid component or a flexible component, and let the total amount of these structural components be 200 mol%.

When the total of the amide structure, imide structure, amic acid structure and urea structure in the polycarbonate imide resin (A) is 100 mol%, it is necessary that the urea structure be 3 mol% or less. Preferably it is 2.8 mol% or less, More preferably, it is 2.6 mol% or less. When the urea structure is 3 mol% or less, excellent solder heat resistance can be expressed. Since it is preferable that the amount of urea structure is small, although a lower limit is not specifically limited, 1 mol% is sufficient. The amount of urea structure depends on the amount of water in the polymerization system and the amidimidization reaction rate, and can be reduced by adding a polymerization catalyst or polymerization in a low moisture absorption solvent. On the other hand, it is preferable that the moisture content in a polymerization system is 1000 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 600 ppm or less, Especially preferably, it is 400 ppm or less. The moisture content in the polymerization system can be reduced by drying the inside of the polymerization system at 150° C. for 2 hours before inputting the raw materials.

Quantification of the urea structure can be performed by ¹ H-NMR measurement with a resonance frequency of 500 MHz and ¹³ C-NMR measurement with a resonance frequency of 125 MHz. The preparation method of the measurement liquid can be performed as follows. For ¹ H-NMR measurement, 10 mg of the sample is dissolved in 0.6 mL of a mixed solvent of heavy chloroform and heavy DMSO (deuterated chloroform / heavy DMSO = 1/1 (volume ratio)) or 0.6 mL of heavy DMSO, and then the solution is The measurement is performed by filling the NMR tube. As for ¹³ C-NMR measurement, 200 mg of a sample is dissolved in 2.7 mL of heavy DMSO, and then the solution is filled in an NMR tube for measurement. In any of the measurements, it is preferable to use heavy DMSO as the lock solvent, and to perform integration 64 times ( ¹ H-NMR) or 1024 times ( ¹³ C-NMR).

Quantification of the urea structure can be calculated as follows. In the heavy chloroform/heavy DMSO mixed solvent of ¹ H-NMR measurement, when the peak of heavy DMSO is 2.5 ppm, the peak around 7.4 ppm is the peak of the imide structure (A), and the peak near 7.7 ppm is the amide structure is the peak (B) of Let A and B be the integral values of each peak. In the heavy DMSO solvent in ¹ H-NMR measurement, when the peak of heavy DMSO is 2.5 ppm, the peak at around 10.6 ppm is the peak of the amide structure (C), and the peak at around 10.4 ppm is the peak of the amic acid structure (D) )to be. Let C and D be the integral values of each peak. ^{In 13} C-NMR measurement, when the peak of heavy DMSO is 40.8 ppm, the peak around 121.8 ppm is the peak of the amide structure (E), and the peak around 119.6 ppm is the peak of the urea structure (F). Let E and F be the integral values of each peak. Using the integral value of the peaks of each structure, the concentration X (mol%) of the urea structure can be expressed by the following formula.

X={(B×F/E)×100}/(A/2+B+B×D/C+B×F/E)

Further, the amic acid structure is preferably 10 mol% or less, more preferably 8 mol% or less, and still more preferably 6 mol% or less from the viewpoint of storage stability of the resin varnish.

The polycarbonate imide resin (A) of the present invention is not particularly limited, but (a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a polycarbonate skeleton represented by the general formula [II] It is preferable that it is a resin which uses as a copolymerization component the acid dianhydride which has, and (c) an isocyanate compound.

<(a) a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group>

As component (a) constituting the polycarbonate imide resin (A) of the present invention, a trivalent and/or tetravalent polycarboxylic acid derivative having an acid anhydride group that generally reacts with an isocyanate component to form a polyimide-based resin. (hereinafter also simply referred to as component (a).) is preferable, and an aromatic polycarboxylic acid derivative, an aliphatic polycarboxylic acid derivative or an alicyclic polycarboxylic acid derivative can be used.

Although it does not specifically limit as an aromatic polycarboxylic acid derivative, For example, trimellitic acid anhydride, pyromellitic dianhydride, ethylene glycol bisanhydro trimellitate, propylene glycol bis anhydrotrimellitate, 1, 4- butanediolbis alkylene glycol bisanhydro trimellitate, such as anhydrotrimellitate, hexamethylene glycol bisanhydrotrimellitate, polyethylene glycol bisanhydro trimellitate, and polypropylene glycol bisanhydro trimellitate, 3,3' -4,4'-benzophenonetetracarboxylic dianhydride, 3,3'-4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3 ,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride Water, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3 -or 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 1,1,1,3 ,3,3-hexafluoro-2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, or 1,3-bis(3,4-di and carboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride.

In addition, the aliphatic or alicyclic polycarboxylic acid derivative is not particularly limited, but for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic acid dianhydride, cyclobutanetetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohexa-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohexa-1- ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3-(1,2),5,6-tetracarboxylic dianhydride; 1-Methyl-3-ethylcyclohexa-1-ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2),3,4 -tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3),3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3), 3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2,2,1]heptane-2,3 ,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3),3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2) ,3),3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2,2,1]heptane -2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,2 ]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydrotrimellitic anhydride, etc. are mentioned.

These trivalent and/or tetravalent polycarboxylic acid derivatives which have an acid anhydride group may be used individually or in combination of 2 or more type. Considering the heat resistance, adhesion, solubility, and cost of the humidified solder, pyromellitic anhydride, trimellitic anhydride, ethylene glycol bisanhydrotrimellitate, 3,3'-4,4'-benzophenonetetracarboxyl Acid dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride are preferable, and trimellitic anhydride and ethylene glycol bisanhydrotrimellitate are more preferable.

The copolymerization amount of component (a) is preferably 10 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% when the total acid component of the reaction target is 100 mol%. % or more and 70 mol% or less are particularly preferred. If it is less than 10 mol%, heat resistance of humidified solder and insulation reliability may not be obtained, and if it is more than 90 mol%, it may not be possible to copolymerize the components (b) and (c) described later in sufficient amounts. Therefore, adhesiveness and solvent solubility may fall.

<(b) acid dianhydride having polycarbonate skeleton represented by general formula [II]>

It is preferable that the component (b) constituting the polycarbonate imide resin (A) of the present invention is an acid dianhydride having a polycarbonate skeleton represented by the general formula [II] (hereinafter also simply referred to as component (b)). . The acid dianhydride of general formula [II] is copolymerized as a flexible component which provides adhesiveness, temporary adhesiveness, etc. to polycarbonate polyimide-type resin (A).

(b) It is preferable that it is an acid dianhydride which has polycarbonate frame|skeleton represented by general formula [II] as a component.

In the general formula [II], a plurality of R each independently represents a divalent organic group having 1 or more carbon atoms. Preferred carbon number is 2 or more, More preferably, it is 4 or more. Moreover, it is preferable that it is 20 or less, More preferably, it is 10 or less, More preferably, it is 8 or less, Especially preferably, it is 6 or less. Specific examples of the divalent organic group having 1 or more carbon atoms are not particularly limited, and aliphatic groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group or octylene group which may have a substituent; Aromatic groups, such as a phenylene group and a biphenylene group, and alicyclic groups, such as a cyclohexylene group, are mentioned. Among these, an aliphatic group is preferable, and n-pentylene group and n-hexylene group are more preferable. Moreover, n is an integer of 1 or more, Preferably it is 2 or more, More preferably, it is 4 or more. An upper limit is not specifically limited, It is preferable that it is 20 or less, More preferably, it is 10 or less. By setting it as the said range, the outstanding adhesiveness and flexibility of polycarbonate-imide resin (A) can be expressed.

The diol compound for synthesizing component (b) used in the present invention is not particularly limited, and for example, aliphatic polycarbonate diols, aromatic polycarbonate diols, and mixtures thereof (manufactured by Daicel Chemical Industries, Ltd., trade name). PLACCEL (registered trademark)-CD220, manufactured by Kuraray Co., Ltd., brand name C-1015N, etc., manufactured by Ube Kosan Co., Ltd., brand name ETERNACOLL (registered trademark)-UH-100, etc., manufactured by Mitsubishi Chemical Co., Ltd., brand name BENEBiOL -NLDB etc., the Asahi Kasei Chemicals Co., Ltd. make, brand name DURANOL-T5651) are mentioned.

Although it does not specifically limit as a method for manufacturing (b) component, It can synthesize|combine by a well-known reaction method from the chloride of trimellitic anhydride, and the above-mentioned diol compound. More specifically, a diol compound and a deoxidizing agent are put into the chloride solution of trimellitic anhydride dissolved in the solvent first, and it stirs for 0.5-24 hours. Although reaction temperature is carried out at -20-50 degreeC, from a viewpoint of reaction selectivity, it is good to carry out more preferably at 20-40 degreeC. As a reaction ratio of the chloride of trimellitic anhydride and a diol compound, it is preferable to make it react using 2 mol or more of the chlorides of trimellitic anhydride with respect to 1 mol of diol compound. The concentration of the solute in the reaction is preferably 5 to 80% by weight, more preferably 40 to 60% by weight. After completion of the reaction, the precipitated hydrochloric acid salt is filtered off and the solvent is concentrated to obtain an acid dianhydride having a polycarbonate skeleton represented by the target general formula [I] (hereinafter also referred to as polycarbonate skeleton-containing tetracarboxylic dianhydride). can get

(b) The copolymerization amount of the component is preferably 15 mol% or more and 90 mol% or less, more preferably 16 mol% or more and 70 mol% or less, when the total acid component of the reaction target is 100 mol%, and 17 mol% or more. % or more and 50 mol% or less are particularly preferred. When less than 15 mol% or more than 90 mol%, there exists a possibility that solvent solubility may fall.

Further, the weight ratio of carbonate diol contained in the component (b) is preferably 18 wt% to 40 wt%, more preferably 20 wt% to 35 wt%, based on the solid content of the adhesive. In the case of less than 18 weight%, the elasticity modulus of an adhesive agent may not fully fall but adhesiveness may fall. On the other hand, when it exceeds 40 weight%, the humidification solder heat resistance of an adhesive agent and insulation reliability may fall.

<(c) isocyanate compound>

The component (c) constituting the polycarbonate imide resin (A) of the present invention is not particularly limited as long as it is an isocyanate compound (hereinafter also simply referred to as component (c)), and aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic poly isocyanate is mentioned. Preferably, an aromatic polyisocyanate is used. Although not particularly limited, specifically, in the aromatic polyisocyanate, for example, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4 ,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3, 2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane -2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-4 ,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4'-[2,2 bis(4-phenoxyphenyl)propane]diisocyanate, 3,3' or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl -4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate, etc. are mentioned. In consideration of heat resistance, adhesion, solubility, cost, etc., diphenylmethane-4,4'-diisocyanate, tolylene-2,4-diisocyanate, m-xylylenediisocyanate, 3,3'- or 2, 2'-dimethylbiphenyl-4,4'-diisocyanate is preferable, and 3,3'-dimethylbiphenyl-4,4'-diisocyanate and tolylene-2,4-diisocyanate are more preferable. These can be used individually or 2 or more types can be used together.

<Other acid components>

You may copolymerize aliphatic, alicyclic, or aromatic polycarboxylic acids with the polycarbonate-imide-type resin (A) of this invention as needed in the range which does not impair the target performance. As the aliphatic dicarboxylic acid, for example, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanoic acid, eicosic acid diacid, 2-methylsuccinic acid, 2-methyladipic acid Acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9 Examples of the alicyclic dicarboxylic acid such as 12-dimethyleicosic acid diacid, fumaric acid, maleic acid, dimer acid, and hydrogenated dimer acid include 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid. Examples of the aromatic dicarboxylic acid such as carboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 4,4'-dicyclohexyldicarboxylic acid include isophthalic acid, terephthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid. , oxydibenzoic acid, stilbenedicarboxylic acid, and the like. These dicarboxylic acids may be used individually or in combination of 2 or more type. In consideration of heat resistance, adhesiveness, solubility, cost, etc., sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, or isophthalic acid is preferable.

Moreover, you may copolymerize other flexible components other than (b) as needed in the range which does not impair the target performance. For example, aliphatic/aromatic polyester diols (manufactured by Toyobo Co., Ltd., trade name VYLON (registered trademark) 200), aliphatic/aromatic polycarbonate diols (manufactured by Daicel Chemical Industries, Ltd., trade name PLACCEL (registered trademark)) -CD220, manufactured by Kuraray, trade name C-2015N, etc.), polycaprolactonediols (manufactured by Daicel Chemical Industries, Ltd., trade name PLACCEL (registered trademark)-220, etc.), carboxy-modified acrylonitrile butadiene and rubbers (manufactured by Ube Kosan Co., Ltd., trade name Hypro CTBN 1300×13, etc.), polysiloxane derivatives such as polydimethylsiloxanediol, polymethylphenylsiloxanediol, and carboxy-modified polydimethylsiloxanes.

As a method for producing the polycarbonate imide resin (A), a method for producing from a polycarboxylic acid component having an acid anhydride group (component (a) and component (b)) and an isocyanate component (component (c)) (isocyanate method) This is preferable. In addition, as the component (c), there is a method of using an amine compound. That is, there is a method (direct method) in which a polycarboxylic acid component having an acid anhydride group (component (a) and component (b)) and an amine component (component (c)) are reacted to form an amic acid, followed by ring closure (direct method). If it is an isocyanate method, since the ring closure process of an amic acid is unnecessary and reaction time can be shortened, it is industrially advantageous.

As for the compounding quantity of (a) component, (b) component, and (c) component, it is preferable that the ratio (the number of isocyanate groups/total number of acid anhydride groups) of the number of isocyanate groups and the total number of acid anhydride groups is less than 1. That is, it is preferable to reduce the number of isocyanate groups with respect to the number of acid anhydride groups. By reducing the number of isocyanate groups, the content of the urea structure can be 3 mol% or less. That is, the urea structure becomes an amine compound when the isocyanate compound decomposes with moisture in the polymerization system, and is formed when the amine compound further reacts with the isocyanate compound. Therefore, decomposition|disassembly of an isocyanate compound can be suppressed by making the number of isocyanate groups less than the number of acid anhydride groups. As for the ratio of the number of isocyanate groups to the number of acid anhydride groups (the number of isocyanate groups/the number of acid anhydride groups), 0.98 or less is more preferable, More preferably, it is 0.95 or less, Especially preferably, it is 0.9 or less. Moreover, although a lower limit is not specifically limited, It is preferable that it is 0.7 or more, More preferably, it is 0.75 or more, More preferably, it is 0.8 or more. If it is less than 0.7, it becomes difficult to make the molecular weight of polycarbonate imide resin (A) high, and a coating film may become weak.

The polymerization reaction of the polycarbonate imide resin (A) used in the present invention is preferably performed by heat-condensing in the presence of one or more organic solvents while removing the free carbon dioxide gas from the reaction system.

As the polymerization solvent, any solvent having low reactivity with isocyanate can be used. For example, a solvent containing no basic compound such as an amine is preferable. Examples of the solvent include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and dipropylene glycol methyl. Ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methylethyl Ketone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, chloroform and methylene chloride and the like.

From the viewpoint of drying volatility, polymer polymerizability, and solubility, the polymerization solvent is preferably N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone or γ-butyrolactone. More preferably, they are N,N- dimethylacetamide and (gamma)-butyrolactone.

It is preferable to set it as 0.8-5.0 times (mass ratio) of the polycarbonate-imide resin (A) to produce, and, as for the usage-amount of a solvent, it is more preferable to set it as 0.9-2.0 times. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and there exists a tendency for synthesis to become difficult due to inability to stir, and when it exceeds 5.0 times, there exists a tendency for the reaction rate to fall.

It is preferable to set it as 60-200 degreeC, and, as for reaction temperature, it is more preferable to set it as 100-180 degreeC. When it is less than 60 degreeC, reaction time becomes too long, and when it exceeds 200 degreeC, decomposition|disassembly of a monomer component may generate|occur|produce during reaction. In addition, a three-dimensional reaction occurs and gelation is likely to occur. The reaction temperature may be performed in multiple steps. The reaction time can be appropriately selected according to the scale of the batch, the reaction conditions employed, and particularly the reaction concentration.

To promote the reaction, triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo[2,2,2]octane), DBU (1,8-diazabicyclo[5) ,4,0]-7-undecene), alkali metals such as lithium methylate, sodium methylate, sodium ethylate, potassium butoxide, potassium fluoride, sodium fluoride, alkaline earth metal compounds, or titanium, cobalt, You may carry out in presence of catalysts, such as metals, such as tin, zinc, and aluminum, and a semimetal compound.

<Production of polycarbonate imide resin (A)>

If an example of the manufacturing method of polycarbonate imide resin (A) is given, (a) component, (b) component, and (c) component can be obtained by condensation reaction (polyimidization). Hereinafter, although the manufacturing method of the polycarbonate imide resin (A) of this invention is illustrated, this invention is not limited by this.

After adding and dissolving component (a), component (b), component (c), polymerization catalyst and polymerization solvent in a reaction vessel, under nitrogen stream, while stirring, at 80 to 190°C, preferably at 100 to 160°C After making it react for 5 hours or more, the target polycarbonate-imide resin (A) can be obtained by diluting to a suitable solvent viscosity with a polymerization solvent, and cooling.

The polycarbonate imide resin (A) of the present invention preferably has a molecular weight corresponding to a logarithmic viscosity of 0.3 to 2.0 dl/g at 30°C, more preferably, it corresponds to a logarithmic viscosity of 0.4 to 1.5 dl/g It has a molecular weight of If the logarithmic viscosity is less than 0.3 dl/g, the B-stage adhesive film may be brittle. Moreover, on the other hand, when it exceeds 2.0 dL/g, it becomes difficult to melt|dissolve in a solvent, and it becomes easy to insolubilize during superposition|polymerization. Moreover, the viscosity of a varnish may become high and handling may become difficult.

Preferably the glass transition temperature of the polycarbonate-imide resin (A) of this invention is 0 degreeC or more, More preferably, it is 20 degreeC or more. If it is less than 0 degreeC, there exists a possibility that humidification solder heat resistance may fall. As for an upper limit, 200 degrees C or less is preferable because it is necessary to provide adhesiveness under general press lamination temperature conditions.

As for the acid value of the polycarbonate imide resin (A) of this invention, 150 eq/t or more is preferable, More preferably, it is 160 eq/t or more, More preferably, it is 180 eq/t or more. When it is too small, the crosslinking density of the coating film after thermosetting may become inadequate, and humidification solder heat resistance and insulation reliability may fall. Moreover, 400 eq/t or less is preferable, More preferably, it is 380 eq/t or less, More preferably, it is 350 eq/t or less. When too large, it becomes difficult to make molecular weight high, and a coating film may become weak.

<Epoxy resin (B) component>

The epoxy resin of (B) component used by this invention will not be specifically limited if it is an epoxy resin which has two or more epoxy groups per molecule. Although it does not specifically limit as an epoxy resin (B), For example, it may modify|denature with silicone, urethane, polyimide, polyamide, etc., and may contain a sulfur atom, a nitrogen atom, etc. in molecular skeleton. For example, glycidyl ether type epoxy resins, such as bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol S type, or what hydrogenated them, phenol novolak type epoxy resin, cresol novolak type epoxy resin, hexa and glycidyl ester-based epoxy resins such as hydrophthalic acid glycidyl ester and dimer acid glycidyl ester, and linear aliphatic epoxy resins such as epoxidized polybutadiene and epoxidized soybean oil. As these commercial items, For example, bisphenol A epoxy resins, such as Mitsubishi Chemical Co., Ltd. brand name jER828, 1001, Hydrogenated bisphenol A, such as a brand name ST-2004 and 2007 by Shin-Nitetsu Sumikin Chemical Co., Ltd. product Bisphenol F-type epoxy resins such as type epoxy resin, EXA-9726 manufactured by DIC Corporation, brand name YDF-170 manufactured by Shin-Nippon Chemical Co., Ltd., and 2004 manufactured by Mitsubishi Chemical Corporation, brand name jER152 manufactured by Mitsubishi Chemical Corporation; 154, brand name DEN-438 manufactured by Dow Chemical Corporation, brand name HP7200, HP7200H manufactured by DIC Corporation, phenol novolak type epoxy resins such as HP7200H, brand name YDCN-700 series manufactured by Nippon-Etsu Sumikin Chemical Co., Ltd., Nippon Gaya Cresol novolak type epoxy resins such as EOCN-125S, 103S, and 104S manufactured by KU Co., Ltd., flexible epoxy resins such as YD-171 manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., Mitsubishi Chemical Co., Ltd. ) manufactured by Epon 1031S, by Chiba Specialty Chemicals Co., Ltd., by brand name Araldite 0163, by Nagase Chemtech Co., Ltd. by brand name Denacol EX-611, EX-614, EX-622, EX-512, Multifunctional epoxy resins, such as EX-521, EX-421, EX-411, EX-321, Mitsubishi Chemical Co., Ltd. product name Epicoat 604, Shin-Nitetsu Sumikin Chemical Co., Ltd. product name YH-434 , Chiba Specialty Chemicals Co., Ltd. brand name Araldite PT810, etc. heterocyclic-containing epoxy resins, Daicel Chemicals Co., Ltd. brand name Celoxide 2021, EHPE3150, UCC Corporation ERL4234, etc. Formula epoxy resins, bisphenol S-type epoxy resins such as Epiclon EXA-1514 manufactured by DIC Corporation, triglycidyl isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd., Mitsubishi Chemical Corporation Bixylenol type epoxy resins, such as brand name YX-4000 of manufacture, bisphenol type epoxy resins, such as Mitsubishi Chemical Corporation brand name YL-6056 etc. are mentioned, These may be used independently and may be used combining plurality.

Among these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin which has more than two epoxy groups in 1 molecule, and o-cresol novolak type epoxy resin are preferable.

The epoxy resin (B) used by this invention may contain the epoxy compound which has only one epoxy group in 1 molecule further as a diluent.

In the following formula 1, 1.1-5.0 are preferable and, as for the usage-amount of the epoxy resin (B) used by this invention, it is more preferable to set it as 1.2-4.0.

Equation 1

Blending ratio of epoxy resin solid content (parts by mass) to adhesive solid content (parts by mass) × epoxy equivalent [eq/t]/{Polycarbonate imide resin (A) solid content (parts by mass) to adhesive solid content (parts by mass) Ratio x acid value of polycarbonate imide resin (A) [eq/t]}

Moreover, when using together the compound which has hydroxyl groups, such as a phosphorus type flame retardant, in following formula 2, 1.1-5.0 are preferable and, as for the usage-amount of an epoxy resin (B), it is more preferable that it is 1.2-4.0.

Equation 2

Blending ratio of epoxy resin solid content (parts by mass) to adhesive solid content (parts by mass) × epoxy equivalent [eq/t]/{Polycarbonate imide resin (A) solid content (parts by mass) to adhesive solid content (parts by mass) Ratio × acid value of polycarbonate imide resin (A) [eq/t] + compounding ratio of compound solid content having a hydroxyl group to adhesive solid content (parts by mass) × hydroxyl value [eq/t]}

In the above calculation formula, when the compounding amount of the epoxy resin (B) is less than 1.1 or exceeds 5.0, the crosslinking density of the coating film after thermosetting becomes insufficient, and the heat resistance of humidified solder and insulation reliability may decrease.

The epoxy equivalent of the epoxy resin (B) is not particularly limited as long as it satisfies Formula 1 or Formula 2, but is preferably 3000 eq/t or more, more preferably 3500 eq/t or more, and still more preferably 4000 more than eq/t. When it is too small, the crosslinking density of the coating film after thermosetting may become inadequate, and humidification solder heat resistance and insulation reliability may fall. Moreover, 10000 eq/t or less is preferable, More preferably, it is 9000 eq/t or less, More preferably, it is 8000 eq/t or less. When too large, the thermosetting reaction of a B-stage adhesive film will advance easily, and there exists a possibility that storage stability may fall.

An epoxy resin (B) generally contains chlorine as an impurity in the manufacturing process. However, it is calculated|required to reduce the amount of halogens from a viewpoint of environmental load reduction, and when there is much chlorine, especially hydrolysable chlorine, it is known that insulation will fall. Therefore, it is preferable that the total amount of chlorine contained in an epoxy resin (B) is 2000 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 1000 ppm or less. Moreover, it is preferable that the total amount of chlorine in the nonvolatile component of an adhesive agent is 500 ppm or less.

<Phosphorus-based flame retardant (C) component>

It is preferable that the resin composition of this invention mix|blends a phosphorus type flame retardant (C) further. By blending the phosphorus-based flame retardant (C), the flame retardancy of the adhesive of the present invention can be improved. The phosphorus-based flame retardant (C) used in the present invention is not particularly limited as long as it contains a phosphorus atom in its structure, but phosphazene or a phosphinic acid derivative is preferable from the viewpoint of hydrolysis resistance, heat resistance and bleed-out. You may use these individually or in combination of 2 or more types.

The phosphazene compound is represented by the following general formula [III] or general formula [IV] (wherein X is the same or different and represents hydrogen, a hydroxyl group, an amino group, an alkyl group, an aryl group, or an organic group, and the organic group includes, for example, an alcohol group, a phenoxy group, an allyl group, a cyanophenoxy group, a hydroxyphenoxy group, etc., n is an integer of 3 to 25).

Commercially available products of these phosphazenes include, for example, cyclic phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., trade names: SPB-100, SPE-100), cyclic cyanophenoxyphosphazene (Co., Ltd.) The Shimi Seiyakusho make, brand name: FP-300), cyclic hydroxyphenoxy phosphazene (the Otsuka Chemical Co., Ltd. product, brand name: SPH-100) etc. are mentioned. These have n=3 as a main component, and have three functional groups which react with an epoxy group. In addition, phosphazenes that do not have a reactive functional group with the epoxy resin (B) cause bleed-out over time, are affected by hydrolysis, etc. under harsh conditions of use, and elute phosphorus in the glass, resulting in a decrease in electrical insulation properties. have. Therefore, a reactive phosphazene having a functional group that reacts with the epoxy resin (B) is preferable. Specifically, the cyclic hydroxyphenoxy phosphazene etc. which have a phenolic hydroxyl group are mentioned.

As the phosphinic acid derivative, a phenanthrene-type phosphinic acid derivative is preferable, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA) , 10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: BCA), 10-(2,5-dihydroxyphenyl)-10- H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ), etc. are mentioned. Among the above-mentioned phosphinic acid derivatives, HCA has reactivity with the epoxy resin (B), but causes bleed-out and may be inferior in high temperature and high humidity resistance. Therefore, it is necessary to appropriately select the compounding amount in consideration of performance. In addition to the phosphorus compound described above, other phosphorus compounds may be used alone or in combination of two or more as needed within a range that does not impair flame retardancy, solder heat resistance and bleed-out.

When the phosphorus-based flame retardant has a hydroxyl group, the hydroxyl value of the phosphorus-based flame retardant is not particularly limited as long as the above formula (2) is satisfied. A preferable hydroxyl value is 4000 eq/t or more, More preferably, it is 4200 eq/t, More preferably, it is 4500 eq/t. Moreover, 7000 eq/t or less is preferable, More preferably, it is 6800 eq/t or less, More preferably, it is 6500 eq/t or less.

As the phosphorus-based flame retardant (C), it is preferable to use (i) a phosphorus-based flame retardant that does not have a functional group that reacts with an epoxy group, and (ii) a phosphorus-based flame retardant that has two or more, particularly three, three functional groups that react with an epoxy group. The ratio of the phosphorus-based flame retardant of (i) and (ii) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2 in terms of mass ratio. When there are many phosphorus flame retardants of (i), there exists a possibility that insulation reliability may fall, and when there are many phosphorus flame retardants of (ii), adhesiveness may fall.

(i) The phosphorus-based flame retardant that does not have a functional group that reacts with the epoxy group has a role of imparting flexibility to the adhesive after thermal curing because it is not incorporated into the crosslinked structure during thermal curing. For example, the above-mentioned cyclic phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., trade name: SPB-100, SPE-100), cyclic cyanophenoxyphosphazene (manufactured by Fushimi Seiyakusho Corporation, trade name: FP- 300), 10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: BCA) or phosphate ester type (manufactured by Daihachi Chemical, trade name: PX-200) and the like. (ii) The phosphorus-based flame retardant having two or more functional groups that react with the epoxy group has a role of suppressing bleed-out and not lowering heat resistance by being incorporated into the cross-linked structure during thermosetting. For example, the aforementioned cyclic hydroxyphenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., trade name: SPH-100), 10-(2,5-dihydroxyphenyl)-10-H-9-oxa-10- Phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name HCA-HQ) and the like fall into this category. Here, when there is only one functional group that reacts with the epoxy, the effect of not lowering the heat resistance of (ii) may become insufficient because it becomes an end of the crosslinked structure and cuts the network.

The compounding quantity of the phosphorus-based flame retardant (C) used in the present invention is preferably used so that the phosphorus content of the adhesive solid content is 1.1 to 5.0, more preferably 1.2 to 4.0. When the phosphorus content of adhesive solid content is less than 1.1, there exists a possibility that a flame retardance may fall, and when it exceeds 5.0, B-stage adhesive film embrittlement resistance may fall.

<Other ingredients>

In the resin composition of the present invention, in addition to the polycarbonate imide resin (A), the epoxy resin (B) and the phosphorus-based flame retardant (C), in order to further improve properties such as adhesion, chemical resistance, and heat resistance, a curing accelerator (polymerization catalyst) ) can be added. As a hardening accelerator used by this invention, what is necessary is just what can accelerate|stimulate the hardening reaction of said polycarbonate imide resin (A) and an epoxy resin (B), and there is no restriction|limiting in particular.

As a specific example of such a hardening accelerator, For example, Shikoku Kasei Kogyo Co., Ltd. product 2MZ, 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ -Imidazole derivatives such as CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ, and guanamines such as acetoguanamine and benzoguanamine , diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polyamines such as polybasic hydrazide, organic acid salts thereof and/ or an epoxy adduct, an amine complex of boron trifluoride, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, etc. of triazine derivatives, trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris( dimethylaminophenol), tetramethylguanidine, DBU (1,8-diazabicyclo[5,4,0]-7-undecene), DBN (1,5-diazabicyclo[4,3,0]-5 tertiary amines such as -nonene), their organic acid salts and/or tetraphenyl boroate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine Organic phosphines such as fin, tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyl tributyl phosphonium chloride, quaternary phosphonium salts such as tetraphenyl phosphonium tetraphenyl boroate , quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride, the polycarboxylic acid anhydride, diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4 Photocationic polymerization catalysts such as 6-triphenylthiopyrylium hexafluorophosphate, Irgacure 261 (manufactured by Chiba Specialty Chemicals Co., Ltd.), and Optomer SP-170 (manufactured by ADEKA Co., Ltd.), styrene - An equimolar reaction product of maleic anhydride resin, phenyl isocyanate and dimethylamine, organic polyisocyanate, such as tolylene diisocyanate, isophorone diisocyanate, and dimethylamine, etc. are mentioned. You may use these individually or in combination of 2 or more types. Preferably, it is a hardening accelerator which has latent curability, and DBU, an organic acid salt of DBN and/or tetraphenyl boroate, a photocationic polymerization catalyst, etc. are mentioned.

When the usage-amount of a hardening accelerator makes polycarbonate imide resin (A) 100 mass parts, 0-20 mass parts is preferable. When it exceeds 20 mass parts, the storage stability of a resin composition and the humidification solder heat resistance of a coating film may fall.

To the resin composition of the present invention, high heat-resistance resin can be added to the resin composition of the present invention in order to improve the insulation reliability under a high temperature and high humidity at a higher level within a range that does not impair the effects of the present invention. As highly heat-resistant resin, it is preferable that a glass transition temperature is resin of 200 degreeC or more, More preferably, it is 250 degreeC or more resin. Although it does not specifically limit, Polyimide resin, polyamideimide resin, polyetherimide resin, polyetheretherketone resin, etc. are mentioned. Moreover, it is preferable that high heat-resistance resin melt|dissolves in a solvent. As what satisfies these conditions, when 100 mol% of the structural unit derived from all acid components is made into 100 mol%, the resin of the anhydride of the polycarboxylic acid which has an aromatic ring is 90 mol% or more, Especially, polyamideimide resin is preferable. is most preferred Specific raw materials are as described above. As a compounding quantity of these high heat-resistant resin, 10-80 mass parts is preferable with respect to 100 mass parts of polycarbonate-imide resins (A), More preferably, it is 20-60 mass parts. When there are too few compounding quantities, an effect is hard to be acquired, and when there are too many, lamination becomes difficult and adhesiveness may fall.

Glycidylamine can be added to the resin composition of this invention in addition to the epoxy resin (B) mentioned above for the purpose of reducing the outflow of the adhesive agent at the time of lamination in the range which does not impair the effect of this invention. The amount of glycidylamine to be added is preferably 0.01 mass% to 5 mass%, more preferably 0.05 mass% to 2 mass%, based on the total weight of the polycarbonate imide resin (A) and the epoxy resin (B) in the adhesive. desirable. When there is too much addition amount of glycidylamine, the fluidity|liquidity of the adhesive agent at the time of lamination may decrease too much, and embedding property of a circuit may fall, and if there is too little addition amount, the effect of sufficient fluidity|liquidity suppression may not be acquired. As glycidylamine, Mitsubishi Gas Chemical Co., Ltd. product name TETRAD-X, TETRAD-C, Nippon Kayaku Co., Ltd. product name GAN, Sumitomo Chemical Co., Ltd. product name ELM-120 etc. are mentioned can be used, and these may be used independently and may be used in combination of plurality.

A silane coupling agent can be added to the resin composition of this invention for the purpose of adhesive improvement, and if it is a conventionally well-known silane coupling agent, it will not specifically limit. Specific examples thereof include aminosilane, mercaptosilane, vinylsilane, epoxysilane, methacrylsilane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof, or a compound obtained by reacting these with polyisocyanate. have. As such a silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropyl Amine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, etc. of aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylethyl Mercaptosilane such as diethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylsilane such as tris-(2-methoxyethoxy)vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β Epoxysilane such as -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldie Methacrylsilane such as toxysilane and 3-methacryloxypropyltriethoxysilane, isocyanate silane such as isocyanatepropyltriethoxysilane and isocyanatepropyltrimethoxysilane, ketiminated propyltrimethoxysilane, and ketiminated propyltriethane Ketimine silanes, such as oxysilane, are mentioned, You may use these individually or in combination of 2 or more types. Since epoxysilane among these silane coupling agents has a reactive epoxy group, it can react with polycarbonate-imide resin, and is preferable at the point of heat resistance and heat-and-moisture resistance improvement. When the compounding quantity of a silane coupling agent makes the whole non-volatile matter of a resin composition 100 mass %, Preferably it is 0-3 mass %, More preferably, it is 0-2 mass %. When a compounding quantity exceeds the said range, humidification solder heat resistance may fall.

An organic/inorganic filler can be added to the resin composition of the present invention for the purpose of improving solder heat resistance within a range that does not impair the effects of the present invention. Examples of the inorganic filler include silica (SiO ₂ , manufactured by Nippon Aerosil Co., Ltd. trade name Aerogel), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), and tantalum oxide (Ta ₂ O ₅ ). , zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO·TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO·TiO ₂ ), lead zirconate titanate (PZT), scattering zirconate titanate Charcoal lead (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO·Al ₂ O ₃ ), mullite (3Al ₂ O ₃ ·2SiO ₂ ), cordierite (2MgO·2Al ₂ O ₃ ·5SiO ₂ ) , talc (3MgO·4SiO ₂ ·H ₂ O), aluminum titanate (TiO ₂ -Al ₂ O ₃ ), yttria-containing zirconia (Y ₂ O ₃ -ZrO ₂ ), barium silicate (BaO·8SiO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C), organic smectite (Trade name Lucentite (trademark) STN, Lucentite SPN, Lucentite SAN, Lucentite SEN by Corp Chemical Co., Ltd. product) etc. can be used, These may be used individually or in combination of 2 or more types.

The inorganic filler used in the present invention preferably has an average particle diameter of 50 μm or less and a maximum particle diameter of 100 μm or less, more preferably an average particle diameter of 20 μm or less, and most preferably an average particle diameter of 10 μm or less. do. The average particle diameter (median diameter) here is a value calculated|required on a volume basis using a laser diffraction/scattering type particle size distribution analyzer. When the average particle diameter exceeds 50 µm, the B-stage adhesive film may become brittle, or poor appearance may occur.

As an organic filler used for this invention, a polyimide resin particle, a benzoguanamine resin particle, an epoxy resin particle, etc. are mentioned.

To the resin composition of the present invention, a silicone-based, fluorine-based, polymer-based defoaming agent, and a leveling agent can be added to the resin composition of the present invention for the purpose of improving the leveling properties and defoaming properties at the time of application within a range that does not impair the effects of the present invention.

<Resin composition (adhesive)>

The resin composition (adhesive) containing the polycarbonate imide resin (A) of the present invention is a composition containing the above-described polycarbonate imide resin (A) component, the epoxy resin (B) component, and the phosphorus-based flame retardant (C) component. Moreover, as needed, other compounding components can be mix|blended preferably in the above-mentioned ratio. Thereby, it can utilize as an adhesive agent suitable for a flexible printed wiring board.

It is preferable that the polycarbonate diol content rate in the whole solid content of a resin composition is 10 weight% or more, More preferably, it is 11 weight% or more, More preferably, it is 12 weight% or more. Moreover, it is preferable that it is 60 weight% or less, More preferably, it is 50 weight% or less, More preferably, it is 40 weight% or less.

The carbonate diol content rate Y (mass %) can be calculated as follows. That is, let the mass of the polycarbonate imide resin (A) be (G), the mass ratio of the component (b) included in the polycarbonate imide resin be (H), and the molecular weight of the component (b) is (J), , (b) When the molecular weight of the polycarbonate skeleton in the component is (K), it can be represented by the following formula.

Y=G×H×K/J

<Adhesive solution>

The adhesive solution in this invention melt|dissolves the said resin composition (adhesive agent) in the said polymerization solvent. The viscosity in a B-type viscometer is preferably in the range of 5 dPa·s to 30 dPa·s, and more preferably in the range of 8 dPa·s to 20 dPa·s at 25°C in the B-type viscometer. When the viscosity is less than 5 dPa·s, the amount of outflow of the solution at the time of application becomes large, and the film thickness tends to decrease. When the viscosity exceeds 30 dPa·s, the leveling property to the substrate tends to decrease during application.

<Adhesive film>

The adhesive solution of this invention can distill off a solvent as follows, for example, and can obtain an adhesive bond film. That is, the polycarbonate imide resin composition solution of the present invention is applied to the release film to a film thickness of 5 to 80 µm by methods such as screen printing, spraying, roll coating, electrostatic coating, and curtain coating, and a coating film is applied. is dried at 60-150° C. for 3-10 minutes, and the solvent is distilled off. Drying may be carried out in an inert atmosphere in air or in an inert atmosphere.

Moreover, in order to adjust the fluidity|liquidity of the adhesive agent at the time of thermocompression bonding, it may heat-process after solvent-drying, and a polycarbonate imide resin and an epoxy resin may be partially reacted. In addition, the state before thermocompression bonding is called a B stage.

As a site|part where an adhesive agent is used in FPC, a CL film, an adhesive film, and a 3-layer copper clad laminated board are mentioned.

In a CL film and an adhesive film, it is common to perform processes, such as winding up, storage, cutting|disconnection, punching, in a B-stage state, and flexibility in a B-stage state is also required. On the other hand, in a three-layer copper clad laminate, it is common to perform thermocompression bonding and thermosetting immediately after B-stage state formation.

Moreover, also in any of the above-mentioned uses, the B-stage adhesive film is thermocompression-bonded with a to-be-adhered body, thermosetting is performed, and it is used.

The CL film consists of an insulating plastic film/adhesive layer or an insulating plastic film/adhesive layer/protective film. The insulating plastic film is a film with a thickness of 1 to 200 μm made of a plastic such as polyimide, polyamide imide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, etc. , a plurality of films selected from these may be laminated. The protective film is not particularly limited as long as it can be peeled off without impairing the properties of the adhesive. For example, polyethylene, polypropylene, polyolefin, polyester, polymethylpentene, polyvinyl chloride, polyvinylidene fluoride, polyphenylene sulfide, etc. plastic films, films coated with silicone or fluoride or other mold release agents, papers laminated with these films, papers impregnated with or coated with a releasable resin, and the like.

The adhesive film has a structure in which a protective film is formed on at least one surface of an adhesive layer made of an adhesive, and has a structure of a protective film/adhesive layer or a protective film/adhesive agent/protective film. In some cases, an insulating plastic film layer is formed in the adhesive layer. The adhesive film can be used for a multilayer printed circuit board.

The three-layer copper-clad laminate has a configuration in which copper foil is bonded to at least one surface of an insulating plastic film with an adhesive. Although copper foil in particular is not restrict|limited, The rolled copper foil and electrolytic copper foil which are conventionally used for a flexible printed wiring board can be used.

Thus, the polycarbonate-imide resin layer of FPC obtained becomes a soldering resist layer of a flexible printed wiring board, a surface protective layer, an interlayer insulating layer, or a contact bonding layer. As described above, the polycarbonate imide resin composition of the present invention is useful as a film forming material for overcoat inks for semiconductor devices and various electronic components, solder resist inks, and interlayer insulating films, and can also be used as a paint, coating agent, adhesive, or the like. Here, the solder resist layer is a film formed on the entire surface of the circuit conductor except for the part to be soldered, and when wiring electronic components on a printed wiring board, it prevents solder from adhering to unnecessary parts, and the circuit is directly exposed to the air. It is used as a protective film to prevent A surface protective layer is used in order to adhere to the surface of a circuit member and to protect an electronic member mechanically and chemically from a processing process and a use environment. An interlayer insulating layer is used in order to prevent electricity from passing between the layers in which the fine wiring in the package board|substrate is formed. An adhesive layer is used mainly when bonding a metal layer and a film layer, and performing a bonding process.

Example

In order to demonstrate this invention more concretely, although an Example is given below, this invention is not limited to an Example at all. In addition, the measured value described in an Example is measured by the following method.

<logarithmic viscosity>

Polycarbonate imide resin (A) was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration was 0.5 g/dL. The solution viscosity and solvent viscosity of the solution were measured at 30° C. by an Uberode-type viscosity tube, and calculated by the following formula.

Logarithmic viscosity (dl/g)=[ln(V1/V2)]/V3

In the above formula, V1 represents the solvent viscosity measured by an Uberode-type viscosity tube, and V1 and V2 are the time the polymer solution and solvent (N-methyl-2-pyrrolidone) pass through the capillary of the viscosity tube. saved from In addition, V3 is a polymer concentration (g/dL).

<mountain>

0.2 g of polycarbonate imide resin (A) was dissolved in 20 ml of N-methylpyrrolidone, titrated with 0.1 N potassium hydroxide ethanol solution, (A) equivalent per 10^6 g of component (equivalent/10^6) g) was found.

<Structural composition and polycarbonate diol content>

For quantitative determination of the urea structure, polycarbonate imide resin (A) varnish was dissolved in CDCl3/DMSO-d (1/1 vol%), and ¹ H-NMR with a resonance frequency of 500 MHz and ¹³ C-NMR with a resonance frequency of 125 MHz. It measured and calculated|required. The amide structure ratio and the imide structure ratio were calculated by ¹ H-NMR measurement, and the urea structure ratio to the amide structure ratio and the amide acid structure ratio to the amide structure ratio were calculated by ¹³ C-NMR measurement. Similarly, the polycarbonate diol content rate in polycarbonate imide resin (A) was also calculated|required by molar ratio, and was converted into content rate (mass %). The preparation method of the measurement liquid was performed as follows. For ¹ H-NMR measurement, 10 mg of the sample is dissolved in 0.6 mL of a mixed solvent of heavy chloroform and heavy DMSO (deuterated chloroform / heavy DMSO = 1/1 (volume ratio)) or 0.6 mL of heavy DMSO, and then the solution is Measurement was carried out by filling an NMR tube. For the ¹³ C-NMR measurement, 200 mg of the sample was dissolved in 2.7 mL of heavy DMSO, and then the solution was filled in an NMR tube for measurement. In any of the measurements, heavy DMSO was used as the lock solvent, and the number of integrations was performed 64 times ( ¹ H-NMR) or 1024 times ( ¹³ C-NMR). As the measurement device, an NMR device AVANCE-500 manufactured by BRUKER was used.

<Calculation method of urea structure concentration>

Quantification of the urea structure was calculated as follows. In the heavy chloroform/heavy DMSO mixed solvent of ¹ H-NMR measurement, when the peak of heavy DMSO is 2.5 ppm, the peak around 7.4 ppm is the peak of the imide structure (A), and the peak near 7.7 ppm is the amide structure is the peak (B) of Let A and B be the integral values of each peak. In the heavy DMSO solvent in ¹ H-NMR measurement, when the peak of heavy DMSO is 2.5 ppm, the peak at around 10.6 ppm is the peak of the amide structure (C), and the peak at around 10.4 ppm is the peak of the amic acid structure (D) )to be. Let C and D be the integral values of each peak. ^{In 13} C-NMR measurement, when the peak of heavy DMSO is 40.8 ppm, the peak around 121.8 ppm is the peak of the amide structure (E), and the peak around 119.6 ppm is the peak of the urea structure (F). Let E and F be the integral values of each peak. Using the integral value of the peaks of each structure, the concentration X (mol%) of the urea structure can be expressed by the following formula.

X={(B×F/E)×100}/(A/2+B+B×D/C+B×F/E)

<Calculation method of carbonate diol content>

The carbonate diol content rate Y (mass %) was calculated as follows. The mass (G) of the polycarbonate imide resin (A), the mass ratio (H) of the component (b) contained in the polycarbonate imide resin (H), the molecular weight of the component (b) (J), the molecular weight of the polycarbonate skeleton in the component (b) When it is set as (K), it can represent with a following formula.

Y=G×H×K/J

<Solvent Solubility>

At the time of polymerization of polycarbonate imide-based resin (A), (a) component, (b) component, (c) component and polymerization solvent are added to the reaction vessel to increase the temperature, and the raw material ( It was evaluated by whether the solution containing (a) component, (b) component, (c) component) was transparent or caused haze.

○: Transparent

x: haze is generated

<Adhesiveness>

The adhesive solution was applied to a polyimide film (Apical 12.5NPI manufactured by Kaneka) to a thickness of 20 µm after drying, and dried at 140°C for 3 minutes with a hot air dryer to obtain a B-stage adhesive film. The adhesive-coated side of this B-stage adhesive film and the glossy side of copper foil (BHY thickness 18 μm, manufactured by JX Nikko Niseki) were thermocompressed under reduced pressure at 160° C., 3 MPa, 30 seconds with a vacuum press laminating machine, and then at 150° C., It was heat-cured for 4 hours. The laminated material after curing was removed by pulling the polyimide film in the direction of 90° at a speed of 50 mm/min in an atmosphere of 25° C. using a tensile tester (Autograph AG-X plus manufactured by Shimadzu), and the adhesive strength was measured. .

(double-circle): adhesive strength 1.0 N/mm or more

○: Adhesive strength 0.8 N/mm or more and less than 1.0 N/mm

(triangle|delta): adhesive strength 0.6 N/mm or more and less than 0.8 N/mm

x: adhesive strength less than 0.6 N/mm

<Insulation Reliability>

A B-stage adhesive film was produced in the same manner as in the adhesive evaluation, and a vacuum press laminating machine was used for a comb pattern of L/S = 50/50 μm, and thermocompression-bonded under reduced pressure at 160° C., 3 MPa, 30 seconds, and then, 150 It was heat-cured at ℃ for 4 hours. A voltage of 200 V was applied for 250 hours under an environment of a temperature of 85°C and a humidity of 85%.

○: Resistance value 1×10 ⁸ Ω or more after 250 hours and no dendrite

×: Resistance value after 250 hours is less than 1×10 ⁸ Ω or there is dendrite

<Heat resistance of humidification solder>

As in the evaluation of adhesiveness, a heat-hardened laminate was prepared, cut to 20 mm in width and length, and after standing for 2 days at a temperature of 40°C and a humidity of 80% RH, it was placed in a 280°C solder bath with the polyimide side facing up. floated.

○: No swelling or peeling;

×: There is swelling or peeling

<flame retardant>

A B-stage adhesive film was prepared similarly to the evaluation of adhesiveness, and the adhesive-coated surface and the polyimide film (Apical 12.5NPI manufactured by Kaneka) were thermocompressed under reduced pressure at 160° C., 3 MPa, and 30 seconds using a vacuum press laminating machine, Then, it heat-hardened at 150 degreeC for 4 hours. The sample after curing was evaluated for flame retardancy in accordance with the UL-94VTM standard.

○: VTM-0 equivalent

x: VTM-0 is not satisfied

<B-stage adhesive film embrittlement>

The adhesive solution was applied to a PET film (E5101, manufactured by Toyobo, having a thickness of 50 µm) to a thickness of 20 µm after drying, and dried with a hot air dryer at 140°C for 3 minutes to obtain a B-stage adhesive film. The adhesive surface was turned 180 degrees outward, and 1 kg of bells were loaded.

○: Cracks do not occur in the adhesive film

×: Cracks occur in the adhesive film

(Production Example 1) (b) Synthesis of acid dianhydride represented by general formula [II]

167 g (0.87 mol) of trimellitic anhydride and thionyl chloride were added to a reaction vessel, and reacted to synthesize a chloride of trimellitic anhydride. Subsequently, 183 g (0.87 mol) of the chloride of trimellitic anhydride and 434 g (0.43 mol) of DURANOL-T5651 (manufactured by Asahi Chemical Co., Ltd., molecular weight 1000) as a diol compound were esterified in toluene at 30°C to form a polycarbonate skeleton The containing tetracarboxylic dianhydride was synthesize|combined.

(Production Example 2)

110.7 g (0.08 mol) of (b) component synthesized in Preparation Example 1, 22.67 g (0.12 mol) of trimellitic anhydride, and 47.55 g (0.19 mol) of 4,4'-diphenylmethane diisocyanate (MDI) as diisocyanate ), 0.30 g of 1,8-diazabicyclo[5,4,0]-7-undecene was added as a polymerization catalyst, and dissolved in 246.29 g of N-methyl-2-pyrrolidone. Then, after reacting at 140°C for 5 hours under nitrogen stream while stirring, 136.83 g of dimethylacetamide was added for dilution, and cooled to room temperature, thereby brown and viscous polycarbonate imide resin solution A having a non-volatile content of 30% by mass. -1 was obtained.

(Production Example 3)

110.7 g (0.08 mol) of (b) component synthesized in Preparation Example 1, 22.67 g (0.12 mol) of trimellitic anhydride, and 46.55 g (0.19 mol) of 4,4'-diphenylmethane diisocyanate (MDI) as diisocyanate ), 0.30 g of 1,8-diazabicyclo[5,4,0]-7-undecene was added as a polymerization catalyst, and dissolved in 245.32 g of γ-butyrolactone. Then, after reacting at 140°C for 5 hours while stirring under a nitrogen stream, 136.29 g of γ-butyrolactone was added for dilution, and the mixture was cooled to room temperature, whereby a brown and viscous polycarbonate imide resin with a non-volatile content of 30 mass% Solution A-2 was obtained.

(Production Example 4)

110.7 g (0.08 mol) of (b) component synthesized in Preparation Example 1, 22.67 g (0.12 mol) of trimellitic anhydride, and 51.55 g (0.21 mol) of 4,4'-diphenylmethane diisocyanate (MDI) as diisocyanate ), 0.30 g of 1,8-diazabicyclo[5,4,0]-7-undecene was added as a polymerization catalyst, and dissolved in 250.19 g of dimethylacetamide. Then, after reacting at 140°C for 5 hours while stirring under a nitrogen stream, 138.99 g of dimethylacetamide was added, diluted, and cooled to room temperature, thereby browning and viscous polycarbonate imide resin solution A having a non-volatile content of 30% by mass. -3 was obtained.

(Preparation Example 5)

110.7 g (0.08 mol) of (b) component synthesized in Preparation Example 1, 22.67 g (0.12 mol) of trimellitic anhydride, and 52.05 g (0.21 mol) of 4,4'-diphenylmethane diisocyanate (MDI) as diisocyanate ) and dissolved in 250.67 g of dimethylacetamide. Then, after reacting at 140°C for 5 hours under nitrogen stream while stirring, 139.26 g of dimethylacetamide was added for dilution, and cooled to room temperature, thereby brown and viscous polycarbonate imide resin solution A having a nonvolatile content of 30% by mass. I got -4.

(Comparative Preparation Example 1)

Synthesized in Preparation Example 1, (b) component 37.80 g (0.03 mol), trimellitic anhydride 33.05 g (0.17 mol), 4,4'-diphenylmethane diisocyanate (MDI) as diisocyanate 47.55 g (0.19 mol) ) and dissolved in 152.51 g of γ-butyrolactone. Then, as a result of making it react at 140 degreeC while stirring under nitrogen stream, it did not melt|dissolve in gamma -butyrolactone, but cloudiness occurred in the solution.

(Examples 1 to 6)

The polycarbonate imide resin (A), the epoxy resin (B), and the flame retardant (C) were mixed in the ratio shown in Table 2 to prepare an adhesive solution, and the above-described characteristic evaluation was performed.

(Comparative Examples 1-2)

It carried out similarly to Example 1, the adhesive agent solution was prepared, and said characteristic evaluation was performed. In both Comparative Example 1 and Comparative Example 2, the urea group concentration contained in the polycarbonate imide resin (A) was higher than 3 mol%. With an increase in the proportion of the urea structure having high hygroscopicity and low heat resistance, the heat resistance of humidified solder decreased. An evaluation result is shown in Table 2.

The polycarbonate imide-based resin paste obtained by the present invention has both excellent heat resistance and flexibility as a film forming material. For this reason, in addition to being useful for overcoat inks for various electronic components such as flexible printed wiring boards, solder resist inks, and interlayer insulating films, it can be used in a wide range of electronic devices as paints, coatings, adhesives, etc., thereby greatly contributing to the industry that is expected

Claims (4)

In the polycarbonate imide resin (A) having the structure described in the general formula [I], the sum of the amide structure, imide structure, amic acid structure, and urea structure in the polycarbonate imide resin (A) was 100 mol% Polycarbonate imide resin (A), characterized in that the content of the urea structure is 3 mol% or less:

(In the general formula [I], a plurality of R is each independently a divalent organic group having 1 or more carbon atoms, and n is an integer of 1 or more.) The polycarbonate imide resin (A) according to claim 1, wherein when the total constituents of the polycarbonate imide resin (A) are 200 mol%, the polycarbonate imide resin (A) contains 15 mol% or more of the structure described in the general formula [I] ). A resin composition comprising the polycarbonate imide resin (A) according to claim 1 or 2, and an epoxy resin (B) having two or more epoxy groups per molecule. The resin composition according to claim 3, further comprising a phosphorus-based flame retardant (C).