JP2007137933A5 - - Google Patents

Description

That is, the present invention includes (A) at least an acid dianhydride residue and a diamine residue, and the diamine residue contains a fluorene-based diamine residue represented by the general formula (1), and has a glass transition temperature of 200 to 200. A resin comprising a polyimide resin in the range of 300 ° C. , (B) an epoxy compound having two or more epoxy groups in one molecule, and (C) a compound having active hydrogen capable of reacting with the epoxy group It is a composition.

In the present invention, when the resin composition was intensively studied as an adhesive for FPC,
(A) At least an acid dianhydride residue and a diamine residue, and the diamine residue contains a residue of a fluorene diamine represented by the general formula (1), and the glass transition temperature is in the range of 200 to 300 ° C. A certain polyimide resin,
(B) an epoxy compound having two or more epoxy groups in one molecule;
(C) a compound having active hydrogen capable of reacting with an epoxy group,
It was found that a heat-resistant resin laminated film excellent in soldering heat resistance and a laminated film with a metal layer can be obtained by using a resin composition containing

In the present invention, the glass transition temperature of the polyimide resin as the component (A) is area by the near of 200 to 320 ° C.. More preferably, it is the range of 220-300 degreeC. When used as an adhesive for FPC, the glass transition temperature is in the range of 200 to 320 ° C., so that the wiring does not sink into the adhesive layer during IC bonding or high-temperature pressing, etc. Becomes better.

Examples 2 to 19
Except having changed the resin solution, the polyimide film, and the copper foil as shown in Table 4, the same operation as in Example 1 was performed to obtain a laminated film with a single-sided copper layer. The polyimide film used here is “Kapton” 100EN (thickness 25 μm) manufactured by Toray DuPont Co., Ltd., and “Apical” 25 NPI (thickness 25 μm) manufactured by Kaneka Corporation. Moreover, the copper foil is a rolled copper foil BHY (thickness 18 μm) manufactured by Nikko Materials Co., Ltd., and the electrolytic copper foil F2-WS (thickness 12 μm) manufactured by Furukawa Circuit Foil Co., Ltd., Japan. This is an electrolytic copper foil USLP (thickness 12 μm) manufactured by Electrolytic Co., Ltd. Table 4 shows the results of adhesive strength, solder heat resistance, glass transition temperature of the heat-resistant resin layer, and bonding resistance of the obtained laminated film with a single-sided copper layer. The peeling interface at the time of adhesive force measurement was all the interface between the polyimide film and the heat resistant resin layer.

Comparative Examples 1 to 25
Except having changed the resin solution, the polyimide film, and the copper foil as shown in Table 4, the same operation as in Example 1 was performed to obtain a laminated film with a single-sided copper layer. Table 4 shows the results of adhesive strength, solder heat resistance, glass transition temperature of the heat-resistant resin layer, and bonding resistance of the obtained laminated film with a single-sided copper layer. The peeling interface at the time of adhesive force measurement was all the interface between the polyimide film and the heat resistant resin layer.

Examples 20-29
Except having changed the resin solution, the polyimide film, and the copper foil as shown in Table 5, the same operation as in Example 1 was performed to obtain a laminated film with a single-sided copper layer. Table 5 shows the adhesive strength, solder heat resistance, glass transition temperature of the heat resistant resin layer, and bonding resistance of the obtained laminated film with a single-sided copper layer. The peeling interface at the time of adhesive force measurement was all the interface between the polyimide film and the heat resistant resin layer.

Example 30
Membrane after drying the resin solution (AP-4) obtained in Production Example 26 on an untreated polyimide film having a thickness of 25 μm (“Kapton” 100EN manufactured by Toray DuPont Co., Ltd.) that has not been surface-treated. After coating with a comma coater to a thickness of 3 μm, drying at 150 ° C. for 2 minutes and at 180 ° C. for 5 minutes, further drying at 230 ° C. for 3 minutes to form a polyimide film / heat-resistant resin layer laminate Obtained.

Examples 31-35
Except having changed the kind and surface treatment of a polyimide film like Table 6, operation similar to Example 30 was performed and the laminated | multilayer film with a single-sided copper layer were obtained. The polyimide film used here is “Kapton” 100EN (thickness 25 μm) manufactured by Toray DuPont Co., Ltd., “Kapton” 100V (thickness 25 μm) manufactured by Toray DuPont Co., Ltd., “UPILEX manufactured by Ube Industries, Ltd. “25S (thickness 25 μm). For the surface treatment, plasma treatment was performed in a carbon dioxide atmosphere using an apparatus capable of continuous treatment in a vacuum chamber.

Claims (12)

(A) At least an acid dianhydride residue and a diamine residue, and the diamine residue contains a residue of a fluorene diamine represented by the general formula (1), and the glass transition temperature is in the range of 200 to 300 ° C. A resin composition comprising a certain polyimide resin, (B) an epoxy compound having two or more epoxy groups in one molecule, and (C) a compound having active hydrogen capable of reacting with an epoxy group.

(R ^{1 to} R ¹⁶ may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen, a hydroxyl group, a carboxyl group, a sulfone group, a nitro group, or a cyano group. Selected from the group.) (A) Polyimide-type resin contains 5-60 mol% of fluorene-type diamine residues represented by General formula (1) in all the diamine residues, The resin composition of Claim 1 characterized by the above-mentioned. (A) Polyimide-type resin contains 2-40 mol% of the siloxane type diamine residue further represented by General formula (2) as a diamine residue in all the diamine residues, The characterized by the above-mentioned. Resin composition.

(N shows the range of 1-30. Moreover, R < ¹⁷ > and R < ¹⁸ > may respectively be the same or different, and shows a C1-C30 alkylene group or a phenylene group. R < ¹⁹ > -R < ²² > is respectively (It may be the same or different and represents an alkyl group having 1 to 30 carbon atoms, a phenyl group or a phenoxy group.) (A) The polyimide resin further contains a residue of one or more aromatic diamines selected from aromatic diamines represented by any one of the general formulas (3) to (5) as a diamine residue. The resin composition according to any one of claims 1 to 3.

(X ¹ is selected from O, CO, S, SO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ , and C (CF ₃ ) _2. X ^{2 to} X ⁴ may be the same or different. , Single bond, O, CO, S, SO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ , and C (CF ₃ ) _2, provided that X ² and X ³ in general formula (4) are In the general formula (5), X ^{2 to} X ⁴ are not all single bonds, and R ^{23 to} R ⁵⁸ may be the same or different, and may be a hydrogen atom or a carbon number of 1 ˜30 alkyl group, C 1-30 alkoxy group, halogen, hydroxyl group, carboxyl group, sulfone group, nitro group, and cyano group. (A) 0.5 to 15 parts by weight of (B) an epoxy compound having two or more epoxy groups in one molecule with respect to 100 parts by weight of a polyimide resin, (C) active hydrogen capable of reacting with an epoxy group The resin composition according to claim 1, comprising 0.1 to 10 parts by weight of a compound containing (A) Polyimide resin is N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N, N ′ 2. The resin composition according to claim 1, which is soluble in at least one organic solvent selected from N, N′-tetramethylurea, dimethyl sulfoxide, γ-butyrolactone, and ethyl lactate. (B) The resin composition according to claim 1, wherein the epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having 3 to 4 epoxy groups in one molecule. A heat-resistant laminated film having a heat-resistant resin layer on at least one side of a heat-resistant insulating film, wherein the heat-resistant resin layer contains the resin composition according to any one of claims 1 to 7 . Resin laminated film. The heat-resistant resin laminated film according to claim 8 , wherein the glass transition temperature of the heat-resistant resin layer is in the range of 200 to 320 ° C. The laminated film with a metal layer which has a metal layer in the heat resistant resin layer side of the heat resistant resin laminated film of Claim 8 or 9 . The wiring board formed by pattern-forming the metal layer of the laminated | multilayer film with a metal layer of Claim 10 . A semiconductor device using the wiring board according to claim 11 .