JP2003012894A - Epoxy resin composition, and insulation resin sheet and printed wiring board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-halogen system epoxy resin composition capable of affording large flame-retardant effect (UL-standard: V-0), an insulation resin sheet using the same and a printed wiring board with excellent solder heat resistance. SOLUTION: This epoxy resin composition comprises (a) a non-halogenated epoxy resin having at least two epoxy groups in a molecule, (b) a phenolic curing agent, (c) a compound having dihydrobenzoxazine ring, (d) a flexibility imparting agent, (e) a polyphenolic antioxidant and (f) a high purity aluminum hydroxide with 0.2 wt.% or less Na2 O content. The insulation resin sheet and the printed wiring board using the composition are provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition, an insulating resin sheet using the same, and a printed wiring board.

[0002]

2. Description of the Related Art With the thinning and miniaturization of consumer electronic devices such as personal computers and mobile phones, the printed wiring boards used for them are thin plates made by a build-up method using resin-coated copper foil corresponding to thinning fine pitch. There is a tendency for higher density and finer wiring such as the practical use of multilayer printed wiring boards. In addition, awareness of environmental issues has increased, and it is necessary to introduce materials that do not generate harmful gases such as dioxins when discarding or incinerating printed wiring boards, especially insulating resin materials that do not use halogen elements (hereinafter referred to as non-halogen type). It is progressing. For this reason, the conventional FR can be applied to a multilayer printed wiring board using a non-halogen insulating resin sheet.
-General properties equivalent to or higher than those of -4 materials are required. In particular,
The method of imparting flame retardancy to the halogen-free insulating resin sheet is the most important item. As a method of imparting flame retardancy, JP-A-6-93191 discloses a flame-retardant non-halogenated epoxy resin composition containing a phosphorus compound, and JP-A-6-93191 discloses a metal oxide and phosphorus. There is a disclosure of a non-halogen flame retardant in which an acid ester is used in combination.
Further, JP-A-9-812925 discloses a non-halogen epoxy resin composition containing aluminum hydroxide as a flame retardant.

[0003]

However, when a phosphorus-based flame retardant such as triphenyl phosphate is blended, the characteristics such as peel strength, glass transition temperature Tg, and chemical resistance of the resin molded product are deteriorated. Moreover, when aluminum hydroxide is added as a flame retardant, the decomposition start temperature of the resin cured product decreases. Therefore, in order to maintain the solder heat resistance of the printed circuit board, it is necessary to limit the amount of aluminum hydroxide compounded, and it is difficult to impart the desired flame retardancy. The present invention provides an epoxy resin composition having excellent flame retardancy (flame retardancy UL standard, flame retardant grade V-0), an insulating resin sheet using the same, and a printed wiring board having excellent solder heat resistance. To do.

[0004]

The gist of the present invention is as follows. [1] (a) Non-halogenated epoxy resin having at least two epoxy groups in one molecule, (b) phenolic curing agent, (c) compound having dihydrobenzoxazine ring, (d) flexibility It is an epoxy resin composition containing an imparting agent, (e) a polyphenolic antioxidant, and (f) a high-purity aluminum hydroxide having a Na ₂ O content of 0.2% by weight or less. [2] In the above item [1], the high-purity aluminum hydroxide is 50 to 120 relative to 100 parts by weight of the total resin solid content.
It is an epoxy resin composition which is part by weight. [3] An insulating resin sheet obtained by applying the epoxy resin composition according to the above item [1] or [2] to at least one main surface of a copper foil or a carrier film and then drying the epoxy resin composition to form an insulating layer. . [4] A method for producing an insulating resin sheet for a multilayer printed wiring board, which comprises applying the epoxy resin composition according to the above item [1] or [2] to a copper foil or a carrier film and then drying it. [5] A prepreg made into a semi-cured state by impregnating a glass woven cloth or a glass non-woven cloth with the epoxy resin composition according to the above [1] or [2] and drying it. [6] A metal foil-clad laminate obtained by stacking a predetermined number of the prepregs according to [5] above, arranging a metal foil on one or both sides of the main surface, and heating and pressing. [7] A printed wiring board obtained by combining the prepreg according to item [5] and the metal foil-clad laminate according to item [6]. [8] A multilayer printed wiring obtained by sequentially combining and laminating the prepreg according to item [5] and the metal foil-clad laminate according to item [6], or the metal foil-clad laminate according to item [6]. It is a plate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples of the present invention will be described in detail. As the (a) epoxy resin that can be used in the present invention, a bifunctional or higher halogen-free epoxy resin can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tree ring type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol A novolac type epoxy resin, polyfunctional phenol diglycone There are di-ether compounds and hydrogenated products thereof, and these can be used alone or in combination. The compounding amount of the curing agent is preferably such that the epoxy resin is in the hydroxyl group equivalent / epoxy equivalent = 0.8 to 1.2 with respect to the hydroxyl group equivalent of the curing agent used.
If it is less than 0.8 or more than 1.2, the heat resistance decreases.

The (b) phenolic curing agent that can be used in the present invention is a phenolic compound having two or more phenolic hydroxyl groups. For example, phenol novolac resin,
Cresol novolac resin, xylene-novolac resin, melamine-novolac resin and the like are preferable, and these can be used alone or in combination of several kinds.

As the compound (c) having a dihydrobenzoxazine ring which can be used in the present invention, a resin system which is cured by a ring-opening reaction of the dihydrobenzoxazine ring can be used. For example, it can be produced from a compound having a phenolic hydroxyl group, formalin and a primary amine. As a compound having a phenolic hydroxyl group,
For example, polyfunctional phenols, polycyclic phenols, and the like, bisphenyl compounds, bisphenol compounds,
A trisphenol compound, a tetraphenol compound and a phenol resin are preferred. Examples of the primary amine include unsubstituted or substituted alkylamine, cycloamine, aniline and the like, and methylamine, cyclohexylamine, aniline, substituted aniline and the like are preferable.

Examples of the flexibility imparting agent (d) used in the present invention include polyvinyl butyral resin and phenoxy resin. The degree of polymerization or the degree of butyralization of the polyvinyl butyral resin is not limited. However, the average degree of polymerization is 500 to 3000, and the degree of butyralization is 60 mo.
It is preferably 1% or more. Furthermore, the average degree of polymerization is 15
0 to 2500, butyralization degree is 65 mol%
The above is more preferable. For example, Eslek B
X-1 (manufactured by Sekisui Chemical Co., Ltd .: average degree of polymerization 1700, butyralization degree 65 mol%), BX-2 (manufactured by Sekisui Chemical Co., Ltd .: average degree of polymerization 1700, 65 mol%), electrified butyral 4000-2 (electrochemical industry) Co., Ltd .: average degree of polymerization 1000, 75 wt%) 5000-A (manufactured by Denki Kagaku Kogyo: average degree of polymerization 2000, 80 wt%)
Etc. These resins can be used alone or in combination of two or more kinds. These polyvinyl butyral resins are preferably added in an amount of 5 to 30 parts by weight based on 100 parts by weight of the total solid varnish. If it is less than 5 parts by weight, the film formability is poor, and if it exceeds 30 parts by weight, flame retardancy,
Heat resistance decreases.

The polyphenol-based antioxidant (e) used in the present invention is preferably a polyphenol having a valence of 3 or more. Furthermore, trihydroxybenzenes are preferable, for example, 1,2,3-trihydroxybenzene, 1,2,4
-Trihydroxybenzene, 1,3,5-trihydroxybenzene. These antioxidants can be used alone or in combination of two or more kinds.
The compounding amount is 0.1 per 100 parts by weight of the total amount of the solid varnish.
Is preferably 5.0 to 5.0 parts by weight, more preferably 0.5 to 2.0 parts by weight. If less than 0.1 parts by weight, no effect is seen,
This is because if it exceeds 5.0 parts by weight, the gel time of the varnish decreases.

The high-purity aluminum hydroxide as the inorganic flame retardant (f) used in the present invention may have a content of impurities Na ₂ O contained in aluminum hydroxide of less than 0.2% by weight. Is not particularly limited. Impurity Na
_If the content of ₂ O is 0.2% by weight or more, the heat resistance decreases. The compounding amount of this high-purity aluminum hydroxide is preferably 50 to 120 parts by weight, more preferably 60 to 100 parts by weight, based on 100 parts by weight of the total resin solid content. If it is less than 50 parts by weight, the flame retardancy is lowered, and if it exceeds 120 parts by weight, the heat resistance is lowered.

If desired, an organic solvent may be added to the epoxy resin composition of the present invention and blended to produce a varnish. As the organic solvent, one that dissolves the resin component excluding the filler can be used. For example, alcohol, acetone, toluene, xylene, ketone, amide,
Examples thereof include pyrrolidone, and preferred are methanol, ethanol, isopropyl alcohol, toluene, methyl ethyl ketone, cyclohexanone, dimethylformamide, and N-methylpyrrolidone. These can be used alone or in combination of two or more.

A diluent may be added, if necessary, in order to improve workability in preparation of the varnish composition of the present invention and coating workability in use. Such diluents include butyl cellosolve, carbitol, butyl cellosolve acetate, carbitol acetate, ethylene glycol diethyl ether, organic solvents having relatively high boiling points such as α-terpineol, PGE (Nippon Kayaku Co., Ltd.), PP-
101 (manufactured by Tohto Kasei Co., Ltd.), ED-502, 503, 50
9 (manufactured by Asahi Denka Co., Ltd.), YED-122 (manufactured by Yuka Shell Epoxy Co., Ltd.), KBM-403, LS-7970 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSL-8350, TSL-8355, T.
Known compounds such as SL-9905 (manufactured by Toshiba Silicone Co.) and the like, such as a reactive diluent having 1 to 2 epoxy groups in one molecule, can be mentioned.

As described above, the varnish obtained according to the present invention is applied to a carrier film, the solvent is removed in the range of 60 to 180 ° C., and the resin is heat-cured to be used for producing an insulating resin sheet. . The coating method is not particularly limited. In the present invention, the carrier film means PET, P
Organic films and copper foils such as BT and PPO that can withstand the drying temperature, and these can be used alone or in combination. A multilayer printed wiring board can be manufactured by arranging and laminating the insulating resin sheet of the present invention on both sides of a circuit-processed double-sided wiring board, and then applying heat and pressure.

When the epoxy resin component itself is liquid, it is possible to obtain a prepreg or laminate material by applying a solventless varnish to each fiber and then heating and drying the organic solvent.

The varnish obtained from the epoxy resin composition of the present invention is applied and impregnated on a fiber base material such as glass woven cloth, glass non-woven cloth, paper, or cloth containing components other than glass fiber at 80 to 200 ° C. A prepreg can be obtained by setting it in a semi-dried state or a semi-cured state. In addition, for the use of materials for laminated boards, E glass, C glass, A glass, S glass, D glass, Q
Various glass cloths such as glass, aramid fiber, carbon fiber, polyester fiber and aramid as organic fiber,
Aromatic polyester sackcloth is used.

The prepreg obtained according to the present invention is heated and pressed at 150 to 200 ° C. and 1.0 to 8.0 MPa to form a metal foil-clad laminate. Similarly,
A printed wiring board can be manufactured by disposing a predetermined number of prepregs between an inner layer base material on which a circuit is formed on a metal foil-clad laminate and a metal foil, and heating and pressing.

Hereinafter, the present invention will be specifically described with reference to examples. [Example 1] Bisphenol F epoxy resin (GK-5
079: manufactured by Nippon Steel Chemical Co., Ltd.) 20 parts by weight (hereinafter referred to as “part”), compound having a dihydrobenzoxazine ring (VR-2000M: manufactured by Hitachi Chemical Co., Ltd.) 70
Part, melamine-modified phenol resin (LA-7054: Dainippon Ink and Chemicals, Inc.) 15 parts, polyvinyl butyral resin (HS-3Z: Sekisui Chemical Co., Ltd.)
15 parts, 60 parts of high-purity aluminum hydroxide (GL-303: manufactured by Sumitomo Chemical Co., Ltd.), 0.5 part of 1,2,3-trihydroxybenzene (pyrogallol: manufactured by Dainippon Pharmaceutical Co., Ltd.), A varnish type epoxy resin composition was obtained by mixing. This resin composition has a thickness of 12
After being applied to a copper foil of μm, it was dried to obtain an insulating resin sheet having a resin thickness of 80 μm. The insulating resin sheet thus obtained was placed on both sides of a base material (RO-67G: manufactured by Hitachi Chemical Co., Ltd., trade name) which was entirely etched, and then the pressure was 3.0M.
A double-sided copper-clad laminate was produced by thermocompression bonding for 90 minutes under the conditions of Pa and heating temperature: 185 ° C.

Example 2 Except that 60 parts of high-purity aluminum hydroxide (same as in Example 1) was replaced with 100 parts,
A double-sided copper-clad laminate was prepared in the same manner as in Example 1.

Comparative Example 1 A double-sided copper-clad laminate was produced in the same manner as in Example 1 except that 60 parts of high-purity aluminum hydroxide (same as in Example 1) was replaced with 40 parts.

[Comparative Example 2] Except that 80 parts of high-purity aluminum hydroxide (same as in Example 1) was replaced with 130 parts,
A double-sided copper-clad laminate was prepared in the same manner as in Example 1.

[Comparative Example 3] The same as Example 1 except that general aluminum hydroxide having a Na ₂ O content of 0.2% by weight was used in place of the high-purity aluminum hydroxide in Example 1. A double-sided copper clad laminate was prepared in the same manner.

After etching the copper foil of the double-sided copper-clad laminate obtained as described above, a flammability test, a solder heat resistance test, and a glass transition temperature Tg were measured. The results are shown in Table 1. The flammability test was performed according to the UL-94 standard. Solder heat resistance test is 50 x 50 mm with full etching
After the moisture absorption treatment (PCT, left for 1,2,3 hours), the test piece was taken out and immersed in a solder bath at 288 ° C. for 20 seconds, and then the presence or absence of swelling of the base material was confirmed. Each symbol in Table 1 is
◯: no change, Δ: occurrence of measling, x: occurrence of swelling, and the three symbols indicate the results evaluated by five test pieces. Moreover, the glass transition temperature Tg is measured by Rheog manufactured by UBM Co., Ltd.
The measurement was performed with an elE-4000 adhesive elasticity measuring device.

[0023]

[Table 1] Table 1

From Table 1, the double-sided copper-clad laminate using the insulating resin sheet of the present invention is UL-94 without using halogen.
V-0 was achieved in the standard flammability test (Examples 1 and 2). The solder heat resistance after the PCT treatment was also good. On the other hand, 50% by weight of total organic resin solids
When it was less than V, V-0 could not be achieved (Comparative Example 1). Further, when it exceeds 120% by weight, the solder heat resistance is significantly lowered (Comparative Example 2). Further, in Comparative Example 3 in which general aluminum hydroxide having a Na ₂ O content of 0.2% by weight in aluminum hydroxide is used, flame retardancy is improved, but solder heat resistance is poor.

[0025]

The epoxy resin composition of the present invention can provide an insulating sheet, a prepreg, and a copper clad laminate for a printed wiring board, which has high flame retardancy without using halogen and has excellent solder heat resistance. it can. Further, since the epoxy resin composition of the present invention does not contain a halogen component that causes generation of harmful substances such as dioxins at the time of combustion, it is an insulating resin sheet and a printed wiring board which correspond to environmental problems. Electronic equipment and electric equipment will be eco-friendly products.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/24 CFC C08J 5/24 CFC C08K 3/22 C08K 3/22 5/13 5/13 5/357 5/357 H01L 23/14 H05K 1/03 610L H05K 1/03 610 H01L 23/14 R (72) Inventor Yoichi Kaneko 1500 Ogawa, Ogawa, Shimodate-shi, Ibaraki Prefecture Hitachi Chemical Co., Ltd. F-term in Shimodate Works (reference) 4F072 AA04 AA07 AB09 AB28 AB29 AD08 AD23 AD42 AE00 AE01 AE10 AF03 AF15 AG03 AH02 AH22 AJ04 AK05 AK14 AL13 4F100 AB17B AB17D AB33B AB33D AK01B AK01D AK19A AK21 AK33A AK33H AK53A AL05A BA02 BA03 BA04 CA02A CA30A DG12C DG15C DH01C EH46A EJ82A EJ91B EJ91D GB43 JG04B JG04D JJ03 JJ07 4J002 BE062 CC042 CC052 CC122 CC182 CD021 CD051 CD061 CD071 CH082 DE148 EJ047 EU236 FD018 FD022 FD077 FD142 G F00 GQ01 4J036 AB07 AC00 AD08 AD20 AF06 AF08 FA03 FA10 FA14 FB02 FB06 FB08 FB09 FB12 JA08

Claims (8)

[Claims] 1. A non-halogenated epoxy resin having at least two epoxy groups in one molecule, (b) a phenolic curing agent, (c) a compound having a dihydrobenzoxazine ring, and (d) a possible. Flexibility-imparting agent, (e) polyphenol-based antioxidant, and (f) Na ₂ O content of 0.2
An epoxy resin composition comprising a high-purity aluminum hydroxide in an amount of not more than 5% by weight. 2. The high-purity aluminum hydroxide according to claim 1, which is 50 to 120 with respect to 100 parts by weight of the total resin solid content.
An epoxy resin composition, characterized in that it is parts by weight. 3. An insulating layer obtained by applying the epoxy resin composition according to claim 1 or 2 to at least one main surface of a copper foil or a carrier film and then drying it. Insulating resin sheet. 4. A method for producing an insulating resin sheet, which comprises producing the epoxy resin composition according to claim 1 or 2 by applying it to a copper foil or a carrier film and then drying it. 5. A prepreg obtained by impregnating a glass woven cloth or a glass non-woven cloth with the epoxy resin composition according to claim 1 or 2 and drying it to a semi-cured state. 6. A metal foil-clad laminate obtained by stacking a predetermined number of the prepregs according to claim 2 or 3 and disposing a metal foil on one side or both sides of the main surface and heating and pressing. 7. A printed wiring board obtained by combining the prepreg according to claim 5 and the metal foil-clad laminate according to claim 6. 8. A multilayer print comprising the prepreg according to claim 5 and the metal foil-clad laminate according to claim 6, or the metal foil-clad laminate according to claim 6, which are sequentially combined and laminated and adhered. Wiring board.