JP2003231762A - Prepreg and laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve glass transition temperature and dielectric characteristics of a halogen-free printed-wiring material compounded with a phosphorus- containing epoxy resin, and to provide a prepreg and a laminated sheet excellent in heat resistance and electric characteristics. <P>SOLUTION: The prepreg is obtained by impregnating or coating a base material with a resin composition (C) comprising as essential ingredients the phosphorus-containing epoxy resin (A) and a cyanate resin (B) and subsequently B-staging it. The laminated sheet for the printed-wiring material is obtained by curing the prepreg. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a prepreg and a laminate for halogen-free printed wiring materials, which are made of a resin composition having excellent heat resistance and electrical characteristics. The resin composition used in the present invention is suitable for use in printed wiring material applications because the obtained cured product has a high glass transition point, excellent dielectric properties, and good moisture absorption heat resistance and flame resistance. .

[0002]

As a printed wiring material for electronic devices,
A prepreg obtained by impregnating a glass cloth with a thermosetting resin such as an epoxy resin type or a BT (bismaleimide-triazine) resin type and heating and drying, a laminated plate obtained by heat curing the prepreg, the laminated plate and the prepreg. Heat-cured multilayer boards in combination with prepregs are widely used.

As a method for making these printed wiring materials flame-retardant, a formulation based on a brominated epoxy resin is generally adopted, but in recent years, various brominated flame retardants have been used due to so-called environmental problems. Regulations have been discussed, and even in epoxy resin-based printed wiring materials, combinations of various flame-retardant compounds have been studied instead of brominated epoxy resins.

In the cases currently proposed, the method of using a phosphorus compound in combination is the mainstream, and in particular, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound, and Although many application examples of phosphorus-containing epoxy resins obtained by reacting a compound with an epoxy resin have been proposed (JP-A-11-124489, 11-166035, 12-802).
51 etc.) In order to respond to the progress of higher density for printed wiring materials, further improvement was required in terms of glass transition point and dielectric properties.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended to improve the glass transition point and dielectric properties of a halogen-free printed wiring material containing a phosphorus-containing epoxy resin. It is an object of the present invention to provide an excellent prepreg and a laminated board.

[0006]

As a result of various studies, the present inventors have found that a laminated material obtained from a resin composition obtained by blending a phosphorus-containing epoxy resin with a cyanate ester resin as a curing agent has a glass transition. The inventors have found that they have excellent points and dielectric properties, and also have good heat resistance after moisture absorption and good flame resistance, and have completed the present invention.

That is, according to the present invention, a substrate is impregnated or coated with a resin composition (C) containing a phosphorus-containing epoxy resin (A) and a cyanate ester resin (B) as essential components, and the B-stage is carried out. Prepreg, which is characterized by
And a laminated board for a printed wiring material obtained by curing the prepreg.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The phosphorus-containing epoxy resin (A) used in the present invention is not particularly limited as long as it is a compound containing a phosphorus atom and an epoxy group. As a typical example, a phosphorus-containing epoxy resin obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with an epoxy resin, 9,10-dihydro
-Oxa-10-phosphaphenanthrene-10-oxide, a phosphorus-containing epoxy resin obtained by reacting a phosphorus-containing compound obtained by the reaction of 1,4 benzoquinone or 1,4 naphthoquinone with an epoxy resin, diphenylphosphine oxide Examples thereof include a phosphorus-containing epoxy resin obtained by a reaction of a phosphorus-containing compound obtained by a reaction of a 1,4-benzoquinone or 1,4 naphthoquinone with an epoxy resin. The phosphorus content of the phosphorus-containing epoxy resin (A) is 0.5 to 8 wt%, preferably 1 to 5 wt%, and the epoxy equivalent is 200 to 1000, preferably 250 to 800.

In the present invention, another epoxy resin may be used in combination within a range that does not impair the desired properties. These are well known and are not particularly limited as long as they are commonly used.

Typical examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin. Resin, biphenyl type epoxy resin, polyol type epoxy resin, alicyclic epoxy resin; polyepoxy compound obtained by epoxidizing double bond such as butadiene,
Examples thereof include a polyglycidyl compound obtained by reacting a hydroxyl group-containing silicone resin with epichlorohydrin, and it is also possible to use one kind or two or more kinds as appropriate as a mixture.

The cyanate ester resin (B) used in the present invention is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule. Specific examples thereof include 1,3- or 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 1,3-, 1,4-,
1,6-, 1,8-, 2,6- or 2,7-dicyanate naphthalene, 1,
3,6-tricyanate naphthalene, 4,4'-dicyanate biphenyl, bis (4-dicyanatephenyl) methane, 2,2-
Bis (4-cyanatephenyl) propane, 4,4'-methylenebis (2,6dimethylphenylcyanate), bis (4-cyanatephenyl) ether, bis (4-cyanatephenyl)
Thioether, bis (4-cyanatephenyl) sulfone,
Tris (4-cyanatephenyl) phosphite, Tris (4
-Cyanatephenyl) phosphate, tetramethylbiphenylcyanate, hexamethylbiphenylcyanate; obtained by the reaction of novolac, phosphorus-containing novolac, hydroxyl-containing thermoplastic resin oligomer (eg, hydroxypolyphenylene ether, hydroxypolystyrene, etc.) with cyanogen halide Cyanates and the like can be mentioned, and one kind or two or more kinds can be appropriately mixed and used.

Further, a prepolymer having a weight average molecular weight of 500 to 5000 and having a triazine ring formed by trimerization of cyanate groups of these cyanate ester compounds is preferably used. The prepolymer is produced by polymerizing the above cyanate ester monomer with a catalyst such as an acid such as a mineral acid or a Lewis acid; a salt such as sodium alcoholate, a salt such as a tertiary amine, or a salt such as sodium carbonate. Is obtained by

The amount of the cyanate ester resin (B) blended is
The total amount of phosphorus-containing epoxy resin (A) and cyanate ester resin (B) is 15 to 75 parts by weight, preferably 20 to 70 parts by weight, per 100 parts by weight.

In the present invention, if necessary, a curing accelerator may be used in combination so as to appropriately adjust the curing rate. These are not particularly limited as long as they are generally used as a curing accelerator for epoxy resins and cyanate ester resins. Typical examples thereof include organic metal salts, imidazoles and their derivatives, and tertiary amines.

The resin composition (C) of the present invention is preferably blended with an inorganic filler (D) in order to further improve flame resistance and laser processability. The inorganic filler D) used is not particularly limited as long as it is an inorganic filler generally used for polymer materials. As typical examples thereof, natural silica, calcined silica, amorphous silica, white carbon, titanium white, aerosil, kaolin, clay, talc, calcined kaolin, calcined clay, calcined talc, wollastonite, natural mica, synthetic mica, Magnesia, alumina, perlite,
Aluminum hydroxide, magnesium hydroxide, molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, glass short fibers, glass fine powder, hollow glass and the like,
It is also possible to use one kind or a mixture of two or more kinds as appropriate. More preferable examples include aluminum hydroxide, calcined talc, and fine glass powder, and the particle size thereof is preferably 20 μm or less. The blending amount of the inorganic filler (D) is from 1 to 100 relative to 100 parts by weight of the blending amount of the phosphorus-containing epoxy resin (A) and the cyanate ester resin (B).
Parts by weight, preferably in the range of 5 to 80 parts by weight.

In the resin composition (C) of the present invention, a flame resistant compound, an additive and the like can be used in combination as long as the desired characteristics are not impaired. These are well known and are not particularly limited as long as they are commonly used. Typical examples of the flame-resistant compound include nitrogen-containing compounds such as melamine and benzoguanamine-modified, oxazine ring-containing compounds, and silicone compounds.Other additives include ultraviolet absorbers such as benzotriazole and hindered phenols. , Antioxidants such as styrenated phenol, photopolymerization initiators such as thioxanthone, fluorescent whitening agents such as stilbene derivatives, photosensitizers, dyes, pigments, thickeners, lubricants, defoamers, dispersants, It is also possible to use a leveling agent, a brightening agent, a polymerization inhibitor, a thixotropic agent, and the like in an appropriate combination as desired.

In the present invention, an organic solvent is used if necessary, but the type thereof is not particularly limited as long as it is compatible with the resin composition (C). Representative examples thereof include acetone, methyl ethyl ketone, methyl cellosolve, propylene glycol methyl ether and its acetate, toluene, xylene, dimethylformamide and the like. They may be used alone or in combination of two or more. When importance is attached to the impregnation property into the substrate, it is preferable to use a solvent having a boiling point of about 120 to 200 ° C. together.

Resin composition (C) containing phosphorus-containing epoxy resin (A) and cyanate ester resin (B) as essential components
Is impregnated or applied to a base material, and is subjected to B stage by heating or the like to produce the prepreg of the present invention. As the base material of the present invention, well-known materials used for various laminated plates for electric insulating materials can be used. Typical examples of the material are E glass, NE glass, D glass, S glass, and Q glass.
Examples thereof include inorganic fibers such as glass, organic fibers such as polyimide and polyester, and a mixture thereof. These base materials include woven fabrics, non-woven fabrics, rovings, chopped strand mats, surfacing mats, etc., depending on their shapes. The material and shape are appropriately selected depending on the intended use and performance of the molded product, and if necessary, one or more materials and shapes can be selected and used. The thickness of the base material is not particularly limited, but usually about 0.03 to 0.5 mm is used. Further, those subjected to surface treatment with a silane coupling agent or the like or those subjected to mechanical fiber opening treatment are suitable from the viewpoint of heat resistance after moisture absorption.

The amount of the resin composition deposited on the substrate is such that the resin content of the prepreg after drying is 30 to 80% by weight. After impregnating or coating the base material, usually 100 to 200
A prepreg of the present invention is obtained by a method of semi-curing (B-stage) by heating for 1 to 30 minutes with a dryer at ℃.

The laminated board of the present invention is formed by laminating using the above-mentioned prepreg of the present invention. Specifically, one or a plurality of the prepregs of the present invention are appropriately stacked, and if desired, a metal foil such as copper or aluminum is placed on one or both surfaces of the prepreg, and the prepreg is laminated and molded. The metal foil is not particularly limited as long as it is used for an electric insulating material, and as a molding condition, a usual laminated plate for electric insulating material and a method of a multilayer plate can be applied. For example, using a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, etc., at a temperature of 100 to 300 ° C.,
The pressure is ² to 100 kg / cm ² , and the heating time is 0.03 to 5 hours. Also, a multilayer board can be manufactured by combining the prepreg of the present invention and a wiring board for an inner layer, which is separately prepared, and laminating and molding.

[0021]

EXAMPLES Example 1 9,10-Dihydro-9-oxa-10-phosphaphenanthrene
Phosphorus-containing epoxy resin obtained by reaction of a phosphorus-containing compound obtained by reaction of -10-oxide with 1,4 benzoquinone and epoxy resin (Epiclon EXA-970
9, epoxy equivalent: 370, phosphorus content: 2.4%, manufactured by Dainippon Ink and Chemicals, Inc. 70 Pre-polymer of 2,2-bis (4-cyanatephenyl) propane (BT207)
0, Mitsubishi Gas Chemical Co., Ltd.) 30 parts by weight, silane coupling agent (Silane A187, manufactured by Nippon Unicar) 1 part by weight was dissolved in dimethylformamide, and then aluminum hydroxide (CL303, manufactured by Sumitomo Chemical) 50 parts by weight, octyl acid A varnish was obtained by mixing 0.02 part by weight of zinc.

This varnish was diluted with methyl ethyl ketone and impregnated and coated on a 0.1 mm thick E glass cloth.
It was heated and dried at 0 ° C. for 6 minutes to obtain a prepreg having a resin content (including an inorganic filler) of 45% by weight. Next, 4 sheets of this prepreg were stacked, and 18 μm electrolytic copper foils were placed on the top and bottom, and pressed at a pressure of 30 kg / cm ² and a temperature of 200 ° C. for 120 minutes to obtain a copper-clad laminate with a thickness of 0.4 mm. It was Table 1 shows the results of measuring the physical properties of the obtained copper-clad laminate.

Example 2 9,10-Dihydro-9-oxa-10-phosphaphenanthrene
Phosphorus-containing epoxy resin obtained by reaction of a phosphorus-containing compound obtained by reaction of -10-oxide with 1,4 benzoquinone and epoxy resin (Epiclon EXA-971
0, epoxy equivalent: 496, phosphorus content: 3.0%, manufactured by Dainippon Ink and Chemicals) 75 parts by weight 2,2-bis (4-cyanatephenyl) propane prepolymer (BT207
0) After dissolving 25 parts by weight in dimethylformamide,
A varnish was obtained by mixing 0.03 part by weight of zinc octylate. Using this varnish, a laminate having a thickness of 0.4 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained copper-clad laminate.

Example 3 Phosphorus-containing epoxy resin (Epiclone EXA-9710)
60 parts by weight, phenol novolac epoxy resin (Epiclon N680, epoxy equivalent: 180, manufactured by Dainippon Ink and Chemicals) 10 parts by weight, 2,2-bis (4-cyanatephenyl) propane prepolymer (BT2070) 30 parts by weight, dispersion After dissolving 1 part by weight of the agent (BYK-111, manufactured by BYK-Chemie) in dimethylformamide, 40 parts by weight of aluminum hydroxide (CL303) and calcined talc (BST
100 parts, made by Nippon Talc) 5 parts by weight, zinc octylate
01 parts by weight were mixed to obtain a varnish. Using this varnish, a laminate having a thickness of 0.4 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained copper-clad laminate.

Example 4 9,10-Dihydro-9-oxa-10-phosphaphenanthrene
A phosphorus-containing epoxy resin (FX289, epoxy equivalent: obtained by reacting a phosphorus-containing compound obtained by reacting -10-oxide with 1,4 naphthoquinone and an epoxy resin
315, phosphorus content: 2.2%, manufactured by Tohto Kasei) 70 parts by weight, novolak cyanate prepolymer obtained from cresol novolac and chlorsian (CT-90, manufactured by Lonza) 25 parts by weight, bisphenol F type epoxy resin ( 5 parts by weight of Epicoat 4001P, epoxy equivalent: 480, manufactured by Japan Epoxy Resin), dissolved in dimethylformamide, and then aluminum hydroxide (CL303) 5
0 parts by weight, E glass powder (PFA-101, Nitto Boseki)
A varnish was obtained by mixing 10 parts by weight of zinc octylate and 0.01 parts by weight. Using this varnish, a laminate having a thickness of 0.4 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained copper-clad laminate.

Example 5 70 parts by weight of phosphorus-containing epoxy resin (FX289) 2,
25 parts by weight of 2-bis (4-cyanatephenyl) propane prepolymer (BT2070), 5 parts by weight of polystyrene oligomer (Picolastec A5, manufactured by Rika Hercules), 2 parts by weight of silane coupling agent (silane A187), dispersant ( After dissolving 0.5 parts by weight of BYK-LPW20084 (manufactured by BYK Chemie) in dimethylformamide, 50 parts by weight of aluminum hydroxide (CL303) and 0.02 parts by weight of zinc octylate were mixed to obtain a varnish.
Using this varnish, a thickness of 0.4 was obtained in the same manner as in Example 1.
A mm laminate was obtained. Table 1 shows the results of measuring the physical properties of the obtained copper-clad laminate.

Comparative Example 75 parts by weight of phosphorus-containing epoxy resin (FX289), phenol novolac resin (Phenolite TD-2131,
After dissolving 25 parts by weight of Dainippon Ink and Chemicals in methyl ethyl ketone, 0.04 parts by weight of dimethylbenzylamine was mixed to obtain a varnish. Using this varnish, a laminate having a thickness of 0.4 mm was obtained in the same manner as in Example 1. Table 1 shows the results of measuring the physical properties of the obtained copper-clad laminate.

[0028]

[Table 1]

Test method: Solder heat resistance, copper foil peel strength, dielectric loss tangent, Tg are according to JIS C6481, and flame resistance is according to UL94 vertical test method.

[0030]

EFFECTS OF THE INVENTION According to the present invention, for an electrically insulating material obtained from a halogen-free resin composition having excellent flame resistance and excellent electric characteristics and heat resistance, which does not generate dioxin or the like when incinerated. Prepregs and laminates are provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/34 C08K 3/34 3/40 3/40 C08L 63/00 C08L 63/00 C 79/00 79 / 00 Z H05K 1/03 610 H05K 1/03 610L 610M 610R F-term (reference) 4F072 AA01 AB05 AB07 AB09 AB28 AB29 AD01 AD32 AF03 AF21 AG03 AH02 AH31 AJ04 AJ15 AL13 4F100 AA19A AB01B AC10A AG00A AK41A AK53A AL05A CA23A DE01A EH46A EJ08A EJ82A GB43 JA07A JJ03 YY00A 4J002 CD15W CM05X DE146 DJ016 DJ036 DJ046 DJ056 DK006 DL006 FA046 FA106 FD04 FD05 FD13 FD13W GQ00 HA05 4J036 AB19 AC20 AD22 AF19 AK13 DC05 DC32 FA02 GA07 JA08 KA01

Claims (8)

[Claims] 1. A resin composition (C) containing a phosphorus-containing epoxy resin (A) and a cyanate ester resin (B) as essential components is impregnated or applied onto a substrate to be B-staged. Characteristic prepreg. 2. An inorganic filler (D) is added to the resin composition (C).
The prepreg according to claim 1, wherein the prepreg is blended. 3. The phosphorus-containing epoxy resin (A) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or 9,10-dihydro-9-oxa-10-phosphaphenanthrene. The prepreg according to claim 1, which is a phosphorus-containing epoxy resin obtained by the reaction of a phosphorus-containing organic compound obtained by the reaction of -10-oxide with a quinone, and an epoxy resin. 4. The prepreg according to claim 1, wherein the cyanate ester resin (B) is a prepolymer having a weight average molecular weight of 500 to 5,000 and having a triazine ring formed by trimerization of cyanate groups. . 5. The inorganic filler (D) is one kind or two or more kinds selected from the group consisting of aluminum hydroxide, calcined talc, and fine glass powder, and is characterized in that Prepreg. 6. The blending amount of the cyanate ester resin (B) is
The prepreg according to claim 1, characterized in that the amount of the phosphorus-containing epoxy resin (A) and the cyanate ester resin (B) is in the range of 15 to 75 parts by weight per 100 parts by weight. 7. The compounding amount of the inorganic filler (D) is 1 to 100 parts by weight based on 100 parts by weight of the phosphorus-containing epoxy resin (A) and cyanate ester resin (B). The prepreg according to claim 2, which is characterized in that: 8. A laminate and a metal-clad laminate for a printed wiring material, which is obtained by curing the prepreg according to claim 1.