JP2003012923A - Thermosetting resin composition and b-stage resin composition sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for printed wiring boards and the like, which is excellent in such characteristics as heat resistance, adhesive properties, flexing properties, migration resistance, electrical insulating properties after a pressure-cooker treatment, and thermal shock resistance. SOLUTION: The thermosetting resin composition is prepared by blending, as essential components, (a) a polyfunctional cyanate ester compound or a prepolymer thereof and (b) a block copolymer composed of a phenolic- hydroxylated aromatic polyamide oligomer having aminoaryl groups at the both ends and a polybutadiene-acrylonitrile copolymer having carboxyl groups at the both ends.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition suitable for adhesives, paints, materials for printed wiring boards, semiconductor encapsulation materials and the like, which has excellent heat resistance and high reliability. Is.

[0002]

2. Description of the Related Art Conventionally, polyfunctional cyanate ester resins have been widely used as materials for printed wiring boards, paints, encapsulating resins, adhesives, etc. because of their excellent heat resistance and electrical properties. However, since it is a heat-resistant resin, the cured product tends to be hard and brittle, and a flexible polyester resin or the like was added to the thermosetting resin in order to improve flexibility, etc. The characteristics were inferior and there was a problem. Also, various additives are added to the epoxy resin to improve flexibility, but in the field of printed wiring boards, etc., where density is becoming higher and higher, heat resistance, electrical insulation after moisture absorption, migration resistance, etc. Was less reliable.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a thermosetting resin composition which is excellent in heat resistance, electrical characteristics, adhesiveness, flexibility, etc. and which has greatly improved the above problems. is there.

[0004]

The present invention provides a thermosetting resin component comprising (a) a polyfunctional cyanate ester compound, the cyanate ester prepolymer and (b) an aminoaryl group at both ends. Use of a thermosetting resin composition comprising a block copolymer formed from an aromatic polyamide oligomer containing a phenolic hydroxyl group and a polybutadiene-acrylonitrile copolymer having carboxyl groups at both end groups as an essential component As a result, brittleness could be improved, and a cured product having excellent flexibility, heat resistance, electrical characteristics, etc. could be obtained.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides, as a thermosetting resin component, (a) a polyfunctional cyanate ester compound, the cyanate ester prepolymer, and (b) a phenolic hydroxyl group having aminoaryl groups at both ends. A thermosetting resin composition comprising a block copolymer formed from an aromatic polyamide oligomer containing and a polybutadiene-acrylonitrile copolymer having carboxyl groups at both end groups as an essential component is used.

The polyfunctional cyanate compound as the component (a) of the present invention is a compound having two or more cyanato groups in the molecule. Specifically, 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3
-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl, bis ( 4-dicyanatophenyl) methane, 2,2-
Bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-Cyanatophenyl) sulfone, Tris
Examples include (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and cyanates obtained by reacting novolac with cyanogen halide. Known compounds having bromine bonded in the molecule can also be used.

In addition to these, Japanese Examined Patent Publications 41-1928 and 43-1846
8, polyfunctional cyanate ester compounds described in JP-A-51-63149 and JP-A-44-4791, JP-A-45-11712, JP-A-46-41112, and JP-A-51-63149 may also be used. Further, a prepolymer having a molecular weight of 200 to 6,000 and having a triazine ring formed by the trimerization of cyanato groups of these polyfunctional cyanate compounds is used. This prepolymer is obtained by polymerizing the above-mentioned polyfunctional cyanate ester monomer using, for example, acids such as mineral acid and Lewis acid; bases such as sodium alcoholate and tertiary amines; salts such as sodium carbonate as a catalyst. It is obtained by This prepolymer also contains some unreacted monomer and is in the form of a mixture of monomer and polymer. Such raw materials are suitably used for the purpose of the present invention. Generally, it is used by dissolving it in a soluble organic solvent. The amount used is generally 20 to 95% by weight, preferably 25 to 70% by weight in the resin component.

The block copolymer (b) of the present invention is disclosed in JP-A-6-2
It is described in Japanese Patent No. 99133 and can be obtained by reacting a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both end groups with a polybutadiene-acrylonitrile copolymer containing both end carboxyl groups. Particularly, the structure represented by Formula 1 is preferably used.

[Chemical 2] (In the formula, p, q, z, r, s, and t are average polymerization degrees, respectively, p = 3 to 7, q = 1 to 4, z = 5 to 15,
1 + s = an integer of 2 to 200, and s / (s + 1) ≧
It is 0.04. )

The phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends used as a raw material is synthesized by condensation polymerization of an aromatic diamine component and an aromatic dicarboxylic acid component. In the present invention, a phenolic hydroxyl group-containing aromatic polyamide oligomer can be produced by mixing an aromatic diamine having a hydroxyl group or an aromatic dicarboxylic acid in the aromatic diamine component or the aromatic dicarboxylic acid component.
Further, both terminal groups of the oligomer can be easily converted into aminoaryl groups by subjecting the aromatic diamine component to a polycondensation reaction in an excess amount over the aromatic dicarboxylic acid component.

Blocking with the polybutadiene-acrylonitrile copolymer having carboxyl groups at both terminals thus synthesized can be similarly synthesized by the above-mentioned polycondensation. This polycondensation can be performed by a conventionally known method. That is, the direct dehydration polycondensation polymerization method of the above-mentioned carboxyl group and amino group, the polymerization method in which the carboxyl group is acid chlorided with thionyl chloride, etc., and then reacted with an amine, and the condensation polymerization catalyst with phosphite ester and pyridine is used. Synthetic methods are preferred.

As the aromatic diamine used for producing the aromatic polyamide oligomer having a phenolic hydroxyl group, m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4'-diaminodiphenyl ether, 3, 3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy -4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,
4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylthioether, 2,
2'-bis (3-aminophenyl) propane, 2,2 '
-Bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine ,
3,3′-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2′-bis (3-aminophenoxyphenyl)
Propane, 2,2'-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4-aminophenoxyphenol) benzene, 1,3'-bis (3-aminophenoxyphenyl) propane, 4,4 ' -(P-phenylenediisopropylidene) bisaniline and the like can be mentioned. These may be used alone or in combination of two or more.

The dicarboxylic acids used for producing the phenolic hydroxyl group-containing aromatic polyamide oligomer of the present invention include, for example, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-oxydibenzoic acid and 4,4 '. -Biphenyldicarboxylic acid, 3,3'-methylenedibenzoic acid, 4,4'-methylenedibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4 '
-Carbonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, etc. To be

Further, as the hydroxyl group-containing aromatic dicarboxylic acid or hydroxyl group-containing aromatic diamine used for introducing a phenolic hydroxyl group into the aromatic polyamide oligomer of the present invention, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 3-
Hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 3,3'-dihydroxy-4,4'-dianiline,
2,2-bis (3'-amino-4-hydroxyphenyl) propane, 2,4-dihydroxy-1,5-diaminobenzene, 5-hydroxy-1,3-diaminobenzene and the like can be used.

A block copolymer (b) formed from a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminal groups and a polybutadiene-acrylonitrile copolymer having both terminal carboxyl groups used in the present invention. Is represented by the structure of the formula [1], but the average degree of polymerization p, q, z, r, s and t is p = 3 to 7 from the viewpoint of the characteristics of the obtained block copolymer. , Q =
1 to 4, z = 5 to 15 and 1 + s = 2 to 200, and preferably s / (s + 1) ≧ 0.04.

In the present invention, the amount of the phenolic hydroxyl group-containing aromatic polyamide and the polybutadiene-acrylonitrile block copolymer (b) used is 0 based on 100 parts by weight of the resin containing the polyfunctional cyanate ester as an essential component. 0.5 to 150 parts by weight, preferably 1 to 100 parts by weight.

Various additives can be added to the thermosetting resin of the present invention, if desired, as long as the original characteristics are not impaired. These additives are not particularly limited, but specifically include: polyfunctional maleimides; unsaturated group-containing polyphenylene ether resins; polyimide resins; liquid and / or solid epoxy resins such as bisphenol A. Type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin,
Polyepoxy compounds obtained by epoxidizing double bonds such as butadiene, pentadiene, vinylcyclohexene, and dicyclopentyl ether, polyols, polyglycidyl compounds obtained by reaction of hydroxyl group-containing silicone resins with epohalohydrin, etc .; Polymerization of unsaturated polyesters, etc. Double bond-containing monomers and prepolymers thereof, allyl compounds, polybutadiene, maleated butadiene,
Butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, acrylic rubber,
Core shell rubbers, etc .; polyethylene, polypropylene,
Examples of polybutene, polystyrene, AS resin, ABS resin, MBS resin, photopolymerizable compound having an ethylenically unsaturated double bond, and the like are used as appropriate. Further, known compounds having bromine bonded in the molecule can also be used. In addition, other known organic and inorganic fillers, dyes, pigments, thickeners,
Various additives such as lubricants, defoamers, dispersants, leveling agents, coupling agents, anti-settling agents, photosensitizers, flame retardants, brighteners, polymerization inhibitors, thixotropy imparting agents, etc. can be added as desired. They may be used alone or in combination of two or more. If necessary, the compound having a reactive group is appropriately mixed with a curing agent and a catalyst.

The thermosetting resin composition of the present invention itself is cured by heating, but since the curing rate is slow and the workability and economy are poor, the known thermosetting resin is used for the thermosetting resin used. A catalyst can be used. The amount used is 0.005 to 10% by weight, preferably 0.010 to 5% by weight. The curing condition of the thermosetting resin composition of the present invention depends on the amount of the catalyst added, but is generally 100 to 200 ° C. and 30 minutes to 5 hours.

The thermosetting resin composition of the present invention is preferably blended with an inorganic filler to improve the performance of making small holes such as carbon dioxide laser. The inorganic filler to be added is not particularly limited, and examples thereof include silica, synthetic silica, talc, calcined talc, silicon nitride, calcium carbonate, barium sulfate, barium titanate-based ceramics, mica, alumina, aluminum hydroxide and the like. Alternatively, two or more kinds are used in combination. The average particle size is preferably 0.5 to 20 μm. In addition, needle-shaped inorganic fillers can also be used. Addition amount is 5
~ 95 wt%, preferably 10-80 wt%. The addition method is a method of adding to the varnish and stirring with a homomixer,
A generally known method such as a method of kneading with a bead mill or a triple roll can be used.

The method for preparing the thermosetting resin of the present invention is as follows:
For example, (a) a polyfunctional cyanate ester compound, the cyanate ester prepolymer, and (b) a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends and a polybutadiene having carboxyl groups at both end groups. Thermosetting resin composition containing a block copolymer formed from an acrylonitrile copolymer as an essential component, a curing catalyst, and various epoxy resins, additives, inorganic fillers, coupling agents, etc., if necessary. Then
After mixing using a Henschel mixer, planetary mixer, etc., uniformly disperse with a triple roll, kneader, etc.,
If necessary, it is pulverized to obtain the thermosetting resin composition of the present invention.

It is also possible to use the above-mentioned composition by dissolving it in a solvent. The solvent used is not particularly limited, for example, N, N-dimethylformamide, N, N-dimethylacetamide, amide solvents such as N-methyl-2-pyrrolidone, diethylene glycol dimethyl ether, ether solvents such as diethylene glycol diethyl ether , Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic hydrocarbon solvents such as toluene and xylene. By using the component (b) of the present invention, it was possible to improve the brittleness and obtain a cured product excellent in flexibility, resistance to thermal shock and the like.

Examples of the metal used in the present invention include generally known metal foils, and electrolytic copper foil, rolled copper foil, nickel foil and the like are preferably used. The thickness is also not particularly limited, but a thickness of 3 to 35 μm is preferably used for a printed wiring board. A generally known film is used as the film, but a polyimide film is preferably used.

The thermosetting resin composition of the present invention is a sheet,
It is applied to one side or both sides of a metal foil or a polyimide film by a known method, heated and dried to remove the solvent, and at the same time, it is B-staged. The method of coating is not particularly limited, but a known method such as gravure coating, spin coating, or screen printing is used. The coating thickness is not particularly limited, but the coating is performed so that the thickness of the resin composition layer after drying becomes 20 to 100 μm. When applying, sheets, films,
After coating on a metal foil, it is dried to form a B-stage, and a protective film is laminated on the resin composition surface. Conversely, a release film is coated and dried to form a B-stage resin composition layer, which is then applied to a sheet. There is a method of adhering to a film or a copper foil under pressure with a heating roll or the like.

When the thermosetting resin composition of the present invention is used as a printed wiring board, it is impregnated into a known inorganic or organic woven or non-woven fabric base material and dried to obtain a B-stage resin composition sheet (prepreg). ), And a copper clad laminate is formed by stacking and laminating copper foils and then forming a printed wiring board by a known method. Further, as a material for build-up, it is also possible to use a B-stage resin composition sheet having no substrate other than the above prepreg, a resin composition sheet with a B-stage copper foil, or the like.

[0024]

The present invention will be specifically described below with reference to Examples and Comparative Examples. Unless otherwise specified, “part” means part by weight. <Component (a): Synthesis of polyfunctional cyanate ester prepolymer> Synthesis example 1 1,000 parts of 2,2-bis (4-cyanatophenyl) propane was added to 150
It was melted at ℃ and reacted for 4 hours with stirring to obtain a prepolymer A having a weight average molecular weight of 1,900. This was dissolved in methyl ethyl ketone to obtain a varnish solution. <Synthesis of Component (b) Block Copolymer>

Synthesis Example 2 A phenolic hydroxyl group-containing aromatic polyamide and a polybutadiene-acrylonitrile copolymer (14 mol% of phenolic hydroxyl group contained in the aromatic polyamide part, referred to as component B) were synthesized by the following method. Isophthalic acid 19.9
3 g (120 mmol), 3,4'-oxydianiline 30.63 g (153 mmol), 5-hydroxyisophthalic acid 3.64 g (20 mmol), lithium chloride 3.9 g, calcium chloride 12.1 g, N-methyl-2
-Pyrrolidone (240 ml) and pyridine (54 ml) were placed in a 1-liter four-necked round bottom flask, and dissolved by stirring. Then, 74 g of triphenyl phosphite was added and reacted at 90 ° C for 4 hours to give a phenolic hydroxyl group-containing aromatic polyamide oligomer. Was generated.

Polybutadiene-acrylonitrile copolymer having both carboxyl groups at both ends (Hycar CTBN, BF
Goodrich, polybutadiene-acrylonitrile component contained in the acrylonitrile component is 17 mol%, molecular weight is about 3600) 48g dissolved in 240 ml of N-methyl-2-pyrrolidone was added, and the reaction was continued for 4 hours, then cooled to room temperature. Then, this reaction solution was added to 20 liters of methanol to prepare an aromatic polyamide and polybutadiene containing about 14 mol% of phenolic hydroxyl groups having a content of the polybutadiene-acrylonitrile copolymer part of 50 wt% used in the present invention. An acrylonitrile block copolymer was deposited. The precipitated polymer was washed with methanol and further refluxed with methanol for purification. The intrinsic viscosity of this polymer is 0.85 dl / g (dimethylformamide,
30 ° C.). When the infrared absorption spectrum of the polymer powder was measured by the diffuse reflection method, it was 1674 cm ^-1.
To the amide carbonyl group at 2856-2975 cm ⁻¹ and the absorption based on the C—H bond of the butadiene moiety at 2245
Absorption based on a nitrile group was observed at cm ^-1 . This polymer is referred to as component B.

Example 1 20 parts of the above B and NMP10 were put into a 500 ml four-necked flask.
5 parts were charged and stirred at room temperature for 24 hours to obtain a block copolymer solution. To this, 20 parts of bis (4-maleimidophenyl) methane was added and dissolved. In this, Synthesis Example 1
200 of polyfunctional cyanate prepolymer A
Part, bisphenol A type epoxy resin (trade name: Epicoat 1001, manufactured by Japan Epoxy Resins Co., Ltd.) 100
Part, cresol novolac type epoxy resin (trade name: EO
A solution prepared by dissolving 150 parts of CN-1025 (manufactured by Nippon Kayaku Co., Ltd.) in methyl ethyl ketone was added and uniformly mixed with stirring. Furthermore, 130 parts of calcined talc (average particle size: 2.5 μm, manufactured by Nippon Talc Co., Ltd.) was added as an inorganic filler, and 0.05 part of zinc octylate was added as a catalyst to this, and the mixture was stirred and dissolved uniformly to give varnish C. And This varnish C is applied to a polyethylene terephthalate (PET) film with a release agent and the resin layer thickness is 80 μm.
Was applied and dried to prepare a B-stage resin composition sheet. This resin layer is a 5 μm thick electrolytic copper foil with a 35 μm protective copper foil (trade name: F3B-WS, with a cobalt alloy treatment on the matte surface, Furukawa Circuit Foil <
Placed on the mat side of the (stock> product), and 6 with a 100 ° C hot roll
A B-stage resin composition sheet D with a copper foil was laminated by laminating at a linear pressure of kgf / cm.

On the other hand, a copper clad laminate (trade name: CCC-HL830,
0.1mm, copper foil 12μm both sides, Mitsubishi Gas Chemical Co., Ltd.)
A mechanical drill is used to open a through hole with a hole diameter of 250 μm.
After desmearing, copper plating was attached to 15 μm, and the inner layer board with line / space = 50/50 μm pattern on the front and back was treated with black copper oxide, and the B-stage resin composition with copper foil on both outer sides Peel off the PET film of the sheet and place it so that the resin side faces the inner layer plate side, place a 2 mm stainless steel plate on the outside, and place cushion paper, 200 ° C, 20 kgf / cm ² , 30 mmHg or less Laminating was performed under vacuum to form a four-layer board. The 35 μm thick protective metal foil on this surface was peeled off, and one shot was irradiated from above the copper clad laminate with a pulse energy of a carbon dioxide gas laser of 10 mJ to form a blind via hole having a hole diameter of 100 μm. After the cobalt alloy treatment of the surface layer is dissolved with a chemical solution, desmear treatment is performed, copper plating is attached to 15 μm, patterns are created on both sides of this, MEC CZ treatment is applied on the copper foil, and general plating is applied on this. A resist was applied and cured, and nickel plating and gold plating were attached. The evaluation results are shown in Table 1.

Example 2 Two B-stage resin composition sheets with copper foil obtained in Example 1 were placed with the resin layers facing each other, and laminated in the same manner as in Example 1 to form a double-sided copper clad board. It was made. The copper foil of this copper clad board is completely removed by etching, and the resin sheet inside has a diameter of
It was wrapped around a 1 mm rod, but no cracks occurred and a resin sheet with excellent flexibility was obtained. Using this copper clad board, a printed wiring board was prepared and evaluated. The results are shown in Table 1.

Example 3 A glass woven cloth having a thickness of 50 μm was impregnated with the varnish C produced in Example 1 and dried to give a gelation time (at 170 ° C.) of 51 seconds,
A B-stage prepreg G having a resin composition content of 65% by weight was produced. One piece was placed on each of both surfaces of the inner layer plate of Example 1, and the protective copper foil used in Example 1 was provided on the outside thereof.
A μm copper foil was placed and laminated in the same manner to produce a four-layer board. After peeling off the protective metal foil on the surface layer, a blind via hole having a hole diameter of 100 μm was formed by directly irradiating one shot with a carbon dioxide gas laser having a pulse energy of 14 mJ. After that, the same processing was performed to obtain a printed wiring board. The evaluation results are shown in Table 1.

Comparative Example 1 In Example 1, a B-stage resin composition sheet with a copper foil was prepared without using the B component, but the B-stage resin layer was fragile, and this was carefully performed so that cracking of the resin did not occur. It was placed on both sides of the inner layer plate of Example 1 and laminated in the same manner to form a four layer plate. During the production of the copper-clad multilayer board, the resin powder was peeled off from the edges and adhered to the copper foil to form a dent. Using this, a printed wiring board was similarly prepared. The evaluation results are shown in Table 1.

Comparative Example 2 Two sheets of the B-stage resin composition sheet with a copper foil of Comparative Example 1 were used.
A sheet and a resin layer were arranged facing each other, and laminated and molded in the same manner as in Comparative Example 1 to produce a double-sided copper clad plate. The copper foil of this copper clad board is completely removed by etching, and the resin composition sheet inside has a diameter of
It was wrapped around a 1 mm rod, but it was brittle and had almost no cracking or bending. An attempt was made to produce a printed wiring board using this copper-clad board, but the resin could not be produced because it cracked. The results are shown in Table 1.
Shown in.

Comparative Example 3 Epoxy resin (trade name: Epicoat 5045, manufactured by Japan Epoxy Resin Co., Ltd.) 700 parts, and epoxy resin (trade name: ESCN
220F, Sumitomo Chemical Co., Ltd.) 300 parts, dicyandiamide 35
Parts, 1 part of 2-ethyl-4-methylimidazole was dissolved in a mixed solvent of methyl ethyl ketone and dimethylformamide, and 300 parts of the calcined talc of Example 1 was further added.
Add the solution prepared by dissolving the component B of the above so that the content of the component B becomes 44 parts. It was forcibly stirred and uniformly dispersed to obtain a varnish E. This was made into a B-stage resin composition sheet F with a copper foil in the same manner as in Example 1. The B-stage resin composition sheet F with a copper foil was similarly arranged above and below the inner layer plate of Example 1, and
A four-layer board was produced by laminating and molding for 2 hours under vacuum at 0 ° C., 20 kgf / cm ² , 30 mmHg or less. Using this, a printed wiring board was prepared in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Measurement method> 1) Solder heat resistance: Pressure cooker (121 ° C, 203kP
(a, 3 hours) After the treatment, it was immersed in a solder bath at 260 ° C for 30 seconds and visually inspected for any abnormality. 2) Glass transition temperature: The copper foil of the double-sided copper clad plate was removed by etching, and this was measured by the DMA method of JIS C6481. 3) Electrical insulation after pressure cooker treatment: A comb-shaped pattern of line / space = 50/50 μm was formed on the inner layer plate, and after black copper oxide treatment was performed, Example 1 was formed on the inner layer plate.
3, the B-stage resin sheets with copper foils of Comparative Examples 1 and 3 were arranged and similarly laminated. This surface copper foil is removed by etching, and this is treated at 121 ° C and 203kPa for a predetermined time, and then left in an atmosphere of 25 ° C and 60% RH for 90 minutes, and then 500V DC is applied for 60 seconds to measure the insulation resistance value. did. 4) Migration resistance: Using the test piece applied to the comb pattern in 3) above, the migration resistance at 85 ° C, 85% RH, and 50VDC application was measured. 5) Blind via hole heat cycle test: Pore diameter 100μm
A land with a diameter of 250 μm is formed in the blind via hole, and 100 holes are alternately connected in series with the inner layer and the surface layer, and 1 cycle is performed at 260 ° C, solder, dipping 30 seconds → room temperature 5 minutes, up to 300 cycles Then, the rate of change in resistance was measured and the maximum value was shown. 6) Thermal shock resistance test: 4 of Examples 1 and 3 and Comparative Examples 1 and 3
The copper foil on the surface of the layered plate is removed by etching, and in a gas phase atmosphere, -65 ℃ / 30min. → room temperature 5min. → + 150 ℃ / 30min. The cross section of the resin crack was observed. The results in Table 1 show that the denominator is the number of tests (1
00), the number of cracks generated in the molecule. 7) Copper foil adhesive strength: It was cut into a width of 10 mm and sandwiched with a Tensilon tester so that the polyimide film and the adhesive were not peeled off, and the copper foil adhesive strength was measured. 8) Adhesive force between polyimide film and adhesive: A test piece in which polyimides were adhered was cut into a width of 10 mm, and the adhesive force between the polyimide film and the adhesive was measured using a Tensilon tester.

(Table 1) Example Comparative Example Item 1 2 3 1 2 3 Soldering heat resistance No abnormality No abnormality No abnormality No abnormality No abnormality Delamination glass transition temperature (° C) -219 220-234 156 Flexibility-Good- over good over insulation resistance (Ω) · 121 ℃, 203kPa normal 5x10 ¹⁴ over 5x10 ¹⁴ 6x10 ¹⁴ over 5x10 ¹⁴ 200hrs. 2x10 ¹⁰ over 1x10 ¹⁰ 3x10 ¹⁰ over ^{<10 8 · 85 ℃, 85} % RH, 50VDC normal 6x10 ¹³ over 5x10 ¹³ 5x10 ¹³ over 5x10 ¹³ 500hrs. 7x10 ¹⁰ over 4x10 ¹⁰ 8x10 ¹⁰ over <10 ⁸ blind via hole heat cycle test (%) 100 cycles 2.2 over 2.0 2.1 over 2.8 300 cycles 2.5 over 2.3 2.7 over 8.7 resistance to thermal shock test (n / 100) 100 cycles 0 / ー 0/0 / ー 0/200 cycles 0 / ー 0/0 / ー 0/300 cycles 0 / ー 0/7 / ー 39/400 cycles 0 / ー 0/15 /ー 70/500 cycles 0 / ー 0/51 / ー 100 /

Examples 4, 5 and 6 The polyfunctional cyanate ester solution obtained in Example 1 (component
A), block copolymer solution (solid component B), epoxy resin (trade name: EOCN-1025, referred to as component X), epoxy resin (trade name: Epicoat 1001, referred to as component Y),
A thermosetting catalyst (zinc octylate, referred to as component P) was blended as shown in Table 2 and dissolved and mixed uniformly, and this varnish was polyimide with a thickness of 50 μm so that the coating film thickness after drying was 30 μm. The film was applied and dried to prepare a film with a B-stage adhesive resin. Place an electrolytic copper foil with a thickness of 18 μm and a polyimide film with a thickness of 50 μm on this resin surface, and
Laminating with a hot roll of 5 kgf / cm linear pressure, 1
It was heat-cured at 20 ° C. for 2 hours, further at 150 ° C. for 1 hour, and at 170 ° C. for 2 hours. This was treated under conditions of 85 ° C. and 85% RH for 24 hours, and the adhesive strength was measured. The adhesive strength at high temperature was also measured. The evaluation results are shown in Table 3.

Comparative Examples 4, 5 and 6 In Example 3, the case where the polyfunctional cyanate ester component A was not used and the case where the block copolymer B was not used were blended as shown in Table 2 and further as a curing agent. Phenol novolac resin (trade name: PN-100, manufactured by Nippon Kayaku Co., Ltd., referred to as component Q), thermosetting catalyst (trade name: 2-methylimidazole,
Shikoku Kasei Co., Ltd., referred to as component R) was mixed, uniformly dissolved and mixed in a solvent, and then similarly coated on a polyimide film and dried to prepare a film with a B-stage adhesive resin. Place an electrolytic copper foil with a thickness of 18 μm and a polyimide film with a thickness of 50 μm on this resin surface, and with a hot roll at 120 ° C., 5 kgf / cm
Laminated at a linear pressure of 2 hours at 120 ° C, then at 150 ° C
It was cured by heating for 1 hour at 170 ° C. for 2 hours. 85 ℃ ・ 85% R
It was treated under the condition of H for 24 hours, and the adhesive force with the copper foil and the polyimide film was measured. The adhesive strength at high temperature was also measured. The evaluation results are shown in Table 3.

Table 2 Examples Comparative Examples Ingredients 4 5 6 4 5 6 A 50 70 100 100 0 0 50 X 20 20 10 0 100 0 20 Y 30 30 20 0 0 100 30 B 30 70 70 90 30 30 70 0 Q 0 0 0 53 16 0 R 0 0 0 1 1 0 P 0.05 0.07 0.10 0 0 0.05

(Table 3) Example Comparative example Measurement item 4 5 6 4 5 6 Copper foil adhesive strength (kgf / cm) Normal condition 0.92 1.20 1.17 0.95 1.26 * 1 85 ° C ・ 85% RH ・ 24hrs. After treatment 0.90 1.15 1.15 0.90 1.10 ー at 100 ℃ 0.89 1.12 1.12 0.54 0.40 ー 150 ℃ 0.83 1.05 1.12 <0.1 <0.1 ー 180 ℃ 0.80 0.72 0.93 0 0 ー Polyimide adhesive strength (kgf / cm) Normal 0.83 1.02 1.07 0.85 1.10 0.1 85 ℃ ・ 85% RH・ After 24hrs. Treatment 0.83 1.00 1.14 0.83 1.06 0 at 100 ℃ 0.79 0.97 1.17 0.20 0.16 ー 150 ℃ 0.73 0.95 1.01 <0.1 <0.1 ー 180 ℃ 0.71 0.60 0.77 0 0 ー * 1: Almost no adhesive strength with polyimide film , Impossible to measure.

[0040]

EFFECTS OF THE INVENTION By using the thermosetting resin composition of the present invention, heat resistance, adhesiveness, flexibility, electrical insulation after pressure cooker, migration resistance, cold heat shock resistance, etc. are excellent. Things have been obtained. Further, the adhesiveness with the polyimide film was also excellent.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 15/31 D06M 15/31 // (C08L 79/00 C08L 77:00 77:00) F term (reference) 4F006 AA39 AB38 AB52 BA01 CA08 DA04 4F072 AA07 AB28 AD02 AD44 AD52 AE16 AF27 AG18 AG19 AJ04 AK05 AL13 4J002 AC112 CL031 CL032 CM051 ET006 GH01 GL00 GQ05 4J031 AA29 AA55 AB01 AC15 CA12 AC26 CA45 AC15 CA15 AC45

Claims (8)

[Claims] 1. A (a) polyfunctional cyanate ester compound, the cyanate ester prepolymer, and (b) a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends and carboxyl groups at both end groups. A thermosetting resin composition comprising a block copolymer formed from the polybutadiene-acrylonitrile copolymer as an essential component. 2. The thermosetting property according to claim 1, wherein the content of the block copolymer is 1 to 100 parts by weight with respect to 100 parts by weight of the resin component essentially containing the polyfunctional cyanate ester. Resin composition. 3. The thermosetting resin composition according to claim 1, wherein the block copolymer is a copolymer represented by [Formula 1]. [Chemical 1] (In the formula, p, q, z, r, s, and t are average polymerization degrees, respectively, p = 3 to 7, q = 1 to 4, z = 5 to 15,
1 + s = an integer of 2 to 200, and s / (s + 1) ≧
It is 0.04. ) 4. A B-stage resin composition sheet having the thermosetting resin composition according to claim 1, 2 or 3 attached to both sides or one side of the sheet. 5. The B-stage resin composition sheet according to claim 4, wherein the sheet is a metal foil. 6. The B-stage resin composition sheet according to claim 4, wherein the sheet is a polyimide film. 7. The sheet is a release film.
The B-stage resin composition sheet described. 8. The B-stage resin composition sheet according to claim 4, wherein the sheet is obtained by impregnating a fiber cloth substrate with a thermosetting resin composition and drying.