JP2002171074A - Built-up multi-layered printed wiring board, and resin composition and resin film used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for built-up, a resin film with a carrier, and a built-up multi-layered printed wiring board which have superior heat resistance, moisture resistance, and anticorrosiveness, without causing hydrogen bromide to be generated as poisonous gas in combustion. SOLUTION: This resin composition for buildup contains (A) thermoplastic resin or thermosetting resin of >=10,000 in weighted mean molecular weight, (B) phosphorus-containing epoxy resin having 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide or its derivative as a reaction component, (C) silicone powder, (D) an inorganic filler, (E) a hardener, and (F) a hardening accelerating agent as essential components and so that the thermoplastic resin or thermosetting resin of (A) is 5 to 80 wt.% of the total weight of (A) to (F) and is applied to buildup of a multi-layered printed wiring board.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention does not use halogen as a flame-retardant method, so that it does not generate toxic gases such as hydrogen bromide, and has a composite of silicone and resin. The present invention relates to a build-up type multilayer printed wiring board exhibiting an extremely high flame retardant effect, and a resin composition and a resin film having excellent heat resistance, moisture resistance and corrosion resistance used for the build-up.

[0002]

2. Description of the Related Art In recent years, with the worldwide concern about environmental issues, especially the safety to the human body, electric and electronic equipments have not only the conventional flame retardancy but also less harmfulness and higher harmfulness. The demand for security is increasing.
That is, it is demanded that electric and electronic devices not only hardly burn, but also generate less harmful gas and harmful dust.

Conventionally, a brominated epoxy resin, for example, a tetrabromobisphenol A type epoxy resin is generally used as an epoxy resin for a printed wiring board made of a glass base epoxy resin on which electric and electronic components are mounted. Although such a brominated epoxy resin has good flame retardancy, it generates harmful hydrogen halide (hydrogen bromide) gas during combustion, and thus its use is being suppressed. on the other hand,
With recent countermeasures, resin films with carriers using epoxy resin that does not contain bromine and the like and build-up type multilayer printed wiring boards are manufactured, but they are more difficult than conventional ones that use brominated epoxy resin. The combustion effect is very poor.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a flame-retardant method which does not use halogen, does not generate toxic gas such as hydrogen bromide during combustion, and further has heat resistance, moisture resistance and corrosion resistance. It is another object of the present invention to provide a resin composition for build-up of a multilayer printed wiring board which exhibits not only an extremely high flame-retardant effect. Further, the present invention provides a resin film with a carrier obtained by coating such a resin composition for build-up on one side of a copper foil or a carrier sheet, and a non-halogen build-up multi-layer print produced using the resin film. It is another object to provide a wiring board.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor did not use a halogen-containing compound as a flame-retardant component in a resin composition for build-up. 9,10-dihydro-9-oxa-10
By using a phosphorus-containing epoxy resin containing -phosphaphenanthrene-10-oxide or a derivative thereof as a reaction component, and further adding silicone powder to form a composite of silicone and resin, the above object is practically achieved. And completed the present invention.

That is, the present invention relates to (A) a thermoplastic resin or a thermosetting resin having a weight average molecular weight of 10,000 or more, and (B) 9,10-dihydro-
9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HCA) or a derivative thereof,
Alternatively, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as HC
A-HQ) or a derivative thereof as one of the reaction components, (C) a silicone powder, (D) an inorganic filler, (E) a curing agent and (F) a curing accelerator as essential components, The thermoplastic resin or the thermosetting resin of (A) is used in an amount of 5 to 5% based on the total weight of (A) to (F).
A resin composition for build-up containing 80% by weight and applied to build-up of a multilayer printed wiring board, and the resin composition for build-up is a copper foil or a carrier sheet. A build-up type multilayer printed wiring board characterized in that a resin film with a carrier coated on one side and this resin film are successively laminated and formed on a glass epoxy laminate as a core.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin or thermosetting resin having a weight average molecular weight of 10,000 or more, which is the component (A) used in the present invention, imparts a film property to the resin composition for build-up, and has an adhesive property and an adhesive property. Those excellent in flexibility are preferable, for example, epoxy resin, phenoxy resin, urethane resin, polyimide resin, polyvinyl butyral, polyvinyl acetal, polyvinyl formal, polyamide, polyacetal, polycarbonate, modified polyphenylene oxide, polybutylene terephthalate, reinforced polyethylene terephthalate, poly Arylate, polysulfone, polyethersulfone, polyetherimide,
Examples thereof include polyamide imide, polyphenylene sulfide, and polyether ether ketone. These resins can be used alone or in combination of two or more. If the weight average molecular weight is less than 10,000, the film forming ability is undesirably reduced.

Further, those having a thermosetting group in a main chain or a side chain, or those having a heat softening point temperature of 90 ° C. or more are preferable for improving heat resistance and moisture resistance, but are not limited thereto. The mixing ratio of the component (A) is 5 to 80% by weight based on the entire resin composition.

The phosphorus-containing epoxy resin (B) used in the present invention uses a polyepoxide compound and a phosphorus compound represented by the following general formula 3 as starting materials, and uses, for example, an aqueous solution of tetramethylammonium chloride as a reaction catalyst. For example, it can be obtained by using a method known as an epoxy resin reaction. In addition, the phosphorus content of the (B) phosphorus-containing epoxy resin must be 0.2 to 8% by weight based on the phosphorus-containing epoxy resin.

[0011]

Embedded image (However, in the formula, R is a hydrogen atom or a substituent other than halogen, and they may be the same or different from each other.) Specifically, for example, the R group in Chemical Formula 3 is a hydrogen atom 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA) and 10-
(2,5-dihydroxyphenyl) -10-hydro-
9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ).

[0012] As the silicone powder (C) used in the present invention, a silicone polymer in which siloxane bonds are three-dimensionally extended into fine particles is used. In particular,
Depending on the shape and particle size of the particles, Tospearl 105, Tospearl 130, Tospearl 240 (trade name, manufactured by GE Toshiba Silicone Co., Ltd.) and the like can be mentioned. The compounding ratio of the silicone powder was 1 part of the resin composition excluding (C) and (D).
When it is set to be 00% by weight, it is added at a ratio of 0.5 to 50% by weight. If it is less than 0.5% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 50% by weight, the resin viscosity increases, and coating unevenness and voids occur, which is not preferable. Further, those having an average particle diameter of 10 μm or less are preferable. If the thickness exceeds 10 μm, the workability is poor because the silicone powder is liable to settle, and the flame retardancy is reduced because the surface area of all the particles is small.

The inorganic filler (D) used in the present invention is not particularly limited, and examples thereof include talc, alumina, aluminum hydroxide, magnesium hydroxide and the like. These can be used alone or in combination of two or more. . The compounding ratio of the inorganic filler is 100 parts of the resin composition excluding the component (D).
In the case where the amount is set to be% by weight, it is preferable to mix in a ratio of 5 to 100% by weight. If the compounding amount is less than 5% by weight, sufficient flame retardancy, heat resistance and moisture resistance cannot be obtained, and if it exceeds 100% by weight, the resin viscosity increases and coating unevenness and voids occur, which is not preferable.

The curing agent (E) used in the present invention can be used without any particular limitation as long as it is a compound usually used for curing an epoxy resin. Examples of amine curing systems include dicyandiamide (DICY) and fragrance. Examples of the phenol curing system include phenol novolak resins, cresol novolak resins, and bisphenol A type novolak resins, and these can be used alone or in combination of two or more.

The (F) curing accelerator is usually
It is used as a curing accelerator for epoxy resins, and examples thereof include imidazole compounds such as 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole. These curing accelerators can be used alone or in combination of two or more.

The resin composition for build-up of the present invention comprises the thermoplastic resin or the thermosetting resin (A) described above,
The phosphorus-containing epoxy resin (B), the silicone powder (C), the inorganic filler (D), the curing agent (E) and the curing accelerator (F) are essential components, provided that they do not violate the object of the present invention. Further, if necessary, a melamine, a guanamine, a melamine resin, a nitrogen-containing compound which can serve as a curing agent such as a guanamine resin and a curing agent can be added and blended.

To use the resin composition for build-up of the present invention in a resin film, the above components (A) to (F) and other components are diluted with a suitable organic solvent such as methyl cellosolve to form a varnish. This can be applied to one side of a carrier sheet such as copper foil or polyester or polyimide, and semi-cured to form a resin film with a carrier by a conventional method. Also, a build-up type multilayer printed wiring board can be obtained by a conventional method such as laminating and molding the resin film with a carrier onto a glass epoxy laminate as a core.

[0018]

The present invention is characterized in that halogen is not used as a flame-retarding method, and does not generate hydrogen bromide, which is a toxic gas during combustion. In addition, the above (A)-
By forming a composite of silicone and resin by combining the component (F), a resin composition exhibiting not only heat resistance, moisture resistance, and corrosion resistance but also an extremely high flame retardant effect is obtained. As a result, a resin film and a build-up type multilayer printed wiring board can be obtained.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[Synthesis Example of Phosphorus-Containing Epoxy Resin] Synthesis Example 1 Bisphenol A type epoxy resin (epoxy equivalent 19
0) 380 g and HCA-HQ (trade name, manufactured by Sanko Chemical Co., Ltd.) [10- (2,5-dihydroxyphenyl) -10
[Hydro-9-oxa-10-phosphaphenanthrene-10-oxide] using 325 g of a reaction catalyst and 0.2 g of tetramethylammonium chloride as an aqueous solution at 170 ° C. for 8 hours to obtain a phosphorus content of 2.9.
% Epoxy resin was synthesized.

Synthesis Example 2 Bisphenol A type epoxy resin (epoxy equivalent 19
0) 380 g and HCA (trade name, manufactured by Sanko Chemical Co., Ltd.)
[9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide] Using 216 g of a reaction catalyst and 0.2 g of tetramethylammonium chloride as an aqueous solution, the mixture was reacted at 170 ° C. for 5 hours to obtain a phosphorus content of 3%. A 2% epoxy resin was synthesized.

Example 1 Epicoat 1256 of a bisphenol A type polymer epoxy resin having a weight average molecular weight of 50,000 (trade name, manufactured by Yuka Shell Co., Ltd., epoxy equivalent: 7,900, resin solid content: 40% by weight)
75 parts, 60 parts of the phosphorus-containing epoxy resin synthesized in Synthesis Example 1 (resin solid content: 75% by weight), dicyandiamide 1.3
Part, silicone powder Tospearl 130 (trade name, manufactured by GE Toshiba Silicone Co., average particle size: 3.0 μm) 15
Parts, aluminum hydroxide 25 parts and 2-ethyl-4-
Methyl cellosolve was added to 0.2 parts of methyl imidazole to prepare an epoxy resin varnish having a resin solid content of 50% by weight.

Example 2 75 parts of Epicoat 1256 (described above) of a bisphenol A type polymer epoxy resin having a weight average molecular weight of 50,000, and the phosphorus-containing epoxy resin synthesized in Synthesis Example 2 (resin solid content of 7
Methyl cellosolve was added to 60 parts of 5 parts by weight), 1.6 parts of dicyandiamide, 15 parts of silicone powder Tospearl 130 (described above), 25 parts of aluminum hydroxide, and 0.2 parts of 2-ethyl-4-methylimidazole. An epoxy resin varnish having a resin solid content of 50% by weight was prepared.

Comparative Example 1 75 parts of Epicoat 1256 (described above) of a bisphenol A type polymer epoxy resin having a weight average molecular weight of 50,000, a brominated epoxy resin (trade name, manufactured by Dainippon Ink and Chemicals, Inc.)
Epoxy equivalent 490) 28 parts, novolak type phenol resin BRG-558 (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 10
6) To 6.1 parts, 25 parts of aluminum hydroxide and 0.2 parts of 2-ethyl-4-methylimidazole, methyl cellosolve was added to prepare an epoxy resin varnish having a resin solid content of 50% by weight.

Comparative Example 2 75 parts of Epicoat 1256 (described above) of a bisphenol A type polymer epoxy resin having a weight average molecular weight of 50,000, 35 parts of a brominated epoxy resin (described above), 0.8 part of dicyandiamide, and 25 parts of aluminum hydroxide To 0.2 part of 2-ethyl-4-methylimidazole was added methyl cellosolve to prepare an epoxy resin varnish having a resin solid content of 50% by weight.

Comparative Example 3 In Example 1, Tospearl 1 of silicone powder was used.
An epoxy resin varnish was prepared in the same manner as in Example 1 except that 15 parts of 30 (trade name, manufactured by GE Toshiba Silicone Co., average particle size: 3.0 μm) were not blended.

Each of the epoxy resin varnishes obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was continuously applied to one surface of a copper foil,
It dried at the temperature of 150 degreeC, and manufactured the resin sheet with a carrier. On both sides of a laminate (Japanese Patent Application No. 11-153204) manufactured in advance using a halogen-free resin composition, the thus obtained resin sheet with a carrier is applied to a laminate.
Heating and pressurizing at a temperature of 40 ° C. and a pressure of 40 MPa for 90 minutes,
A build-up type multilayer printed wiring board having a thickness of 0.6 mm was obtained.

The resulting build-up type multilayer printed wiring board was measured for flame retardancy, heat resistance and moisture resistance and analyzed for combustion gas. The results are shown in Table 1. The resin composition for build-up of the present invention, the build-up type multilayer printed wiring board using the resin film is not inferior to those using the conventional brominated epoxy resin in any of the characteristics, and also has a long term As for the peel strength of deterioration, good results were obtained because bromine was not contained. on the other hand,
It was confirmed that there was no generation of hydrogen bromide, which is a problem during combustion.

[0029]

[Table 1] * 1: Measured according to UL94 flame retardancy test.

* 2: Measured according to IEC-PB112.

* 3: Measured according to JIS-C-6481.

* 4: The samples were floated on the solder bath at 260 ° C. for each time shown in the table, and the presence or absence of swelling was observed, and evaluated according to the following criteria. ◎: no swelling, ○: some swelling, △
Mark: Mostly swollen, x: All swollen.

* 5: After the sample was treated under the condition A (boiled for 2 hours) or the condition B (boiled for 4 hours), it was immersed in a solder bath at 260 ° C. for 30 seconds, and observed for blistering. The evaluation was based on the following criteria. ◎: no swelling, ○: partial swelling, Δ: large swelling, ×: all swelling.

* 6: Each sample was burned in air at 750 ° C. for 10 minutes, and the gas generated at that time was absorbed in an absorbing solution and analyzed by ion chromatography.

[0035]

As is clear from the above description and Table 1, the present invention is characterized in that halogen is not used as a flame retarding method, and toxic gas such as hydrogen bromide is generated during combustion. I will not let you. Furthermore, (A) ~
By forming a composite of silicone and resin by combining the component (F), a resin composition is provided which exhibits not only heat resistance, moisture resistance, and corrosion resistance but also extremely high flame retardancy. Thereby, a resin film with a carrier and a build-up type multilayer printed wiring board having excellent heat resistance and moisture resistance can be manufactured.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) C08L 63/00 C08L 63/00 AC 83/04 83/04 101/00 101/00 F-term (reference) 4F071 AA03 AA42 AB18 AB26 AE02 AE17 AH13 BA02 BB02 BC01 BC02 4J002 AA022 CD111 CD201 CP033 DE076 DE146 DJ046 FD016 FD140 FD150 GQ01 4J036 AJ00 CC02 DC02 DC41 FA01 FB01 FB07 FB11 FB12 CC12 FB13 A12 CCB EE31 GG02 HH13 HH16

Claims (6)

[Claims] (1) a thermoplastic resin or a thermosetting resin having a weight average molecular weight of 10,000 or more; (B) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 represented by the following general formula: -Oxide or derivative thereof (Wherein, R is a hydrogen atom or a substituent other than halogen, and they may be the same or different from each other) or 10- (2,5-dihydroxyphenyl) -10 shown in the following general formula -Hydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof (Wherein, R is a hydrogen atom or a substituent other than halogen, and they may be the same or different from each other).
(C) silicone powder, (D) inorganic filler, (E)
(A) a curing agent and (F) a curing accelerator as essential components;
Thermoplastic resins or thermosetting resins of (A) to (F)
Characterized in that it is contained in a proportion of 5 to 80% by weight based on the total weight of the resin composition, and is applied to build-up of a multilayer printed wiring board. 2. The build-up resin composition according to claim 1, wherein the phosphorus content of the phosphorus-containing epoxy resin (B) is 0.2 to 8% by weight. 3. The silicone powder (C) is a finely divided silicone polymer having three-dimensionally extended siloxane bonds, and the compounding ratio thereof is 100 weight% of the resin composition other than (C) and (D). %, 0.5 to 50
The resin composition for build-up according to claim 1 or 2, which is a percentage by weight. 4. The inorganic filler (D) is selected from the group consisting of talc, alumina, aluminum hydroxide and magnesium hydroxide, and its compounding ratio is 100% by weight of the resin composition excluding the component (D). The resin composition for build-up according to claim 1, wherein the ratio is 5 to 100% by weight. 5. A resin film with a carrier, wherein the resin composition for build-up according to claim 1 is coated on one side of a copper foil or a carrier sheet. 6. A build-up type multilayer printed wiring board, wherein the resin film according to claim 5 is successively laminated and formed on a glass epoxy laminated board as a core.