JP3403987B2 - Build-up type multilayer printed wiring board, resin composition and resin film used therefor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention does not use halogen as a flame retardant technique and therefore does not generate a toxic gas such as hydrogen bromide during combustion, and a build-up type multilayer printed wiring board and its build. The present invention relates to a resin composition and a resin film having excellent heat resistance, moisture resistance, and corrosion resistance used for cleaning up.

[0002]

2. Description of the Related Art In recent years, with the increasing worldwide concern about environmental problems, especially safety for humans,
With respect to electronic devices, in addition to the conventional flame retardancy, there is an increasing demand for less harmful effects and higher safety. That is, electric / electronic devices are required not only to be difficult to burn but also to generate less harmful gas and harmful dust. Conventionally, a brominated epoxy resin containing bromine, which is a flame retardant, such as tetrabromobisphenol A type epoxy resin is generally used as an epoxy resin for a printed wiring board of a glass-based epoxy resin on which electric / electronic components are mounted. .

Although such a brominated epoxy resin has good flame retardancy, its use is being suppressed because it produces harmful hydrogen halide (hydrogen bromide) gas during combustion.

[0004]

The object of the present invention is to provide excellent heat resistance, moisture resistance and corrosion resistance without using halogen as a flame retardant technique and without producing toxic gases such as hydrogen bromide during combustion. Another object of the present invention is to provide a resin composition for buildup of a multilayer printed wiring board. Furthermore, the present invention provides a resin film with a carrier obtained by coating such a build-up resin composition on one side of a copper foil or a carrier sheet, and a non-halogen build-up type multilayer print produced using this resin film. It is also an object to provide a wiring board.

[0005]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that a halogen-containing compound was not used as a flame retardant in a resin composition for build-up. By using an epoxy resin containing 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof as a reaction component,
The present invention has been completed by finding that the above object is practically achieved.

That is, the present invention provides (A) an epoxy having a weight average molecular weight of 10,000 or more.
Resin (provided that the epoxy equivalent is 500 or less
Functional epoxy resin is excluded) , (B) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound (hereinafter, referred to as H
CA), or 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide compound (hereinafter referred to as HC
(A-HQ) is one of the reaction components, a phosphorus-containing epoxy resin, (C) an inorganic filler, (D) a curing agent and (E) a curing accelerator are essential components, and the epoxy resin of (A) is ( A) ~
A resin composition for build-up, characterized in that the resin composition is contained in a proportion of 5 to 70% by weight with respect to the total weight of (E), and is applied to build-up of a multilayer printed wiring board. A resin film with carrier formed by coating a resin composition for use on one side of a copper foil or a carrier sheet, and a build-up type multi-layer formed by successively laminating and molding this resin film on a glass epoxy laminated plate serving as a core It is a printed wiring board.

The present invention will be described in detail below.

The high molecular weight resin having a weight average molecular weight of 10,000 or more, which is the component (A) used in the present invention, imparts film property to the resin composition for build-up and is excellent in adhesiveness and flexibility. Preferred are, 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, polyarylate, polysulfone, poly. Examples thereof include ether sulfone, polyether imide, polyamide imide, polyphenylene sulfide, and polyether ether ketone. These resins may be used alone or in combination of two or more kinds. Can. Weight average molecular weight is 1
If it is less than 0000, the film forming ability is lowered, which is not preferable.

Further, those having a thermosetting group in the main chain or side chain, or those having a thermal softening point temperature of 90 ° C. or higher are preferable but not limited in terms of improving heat resistance and moisture resistance. The blending ratio of the component (A) is 5 to 70% by weight based on the whole 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 5 as starting materials, and uses, for example, an aqueous solution of tetramethylammonium chloride as a reaction catalyst. Etc. can be obtained by using a known method such as an epoxy resin reaction. The phosphorus content of the (B) phosphorus-containing epoxy resin needs to be 0.2 to 8% by weight with respect to the phosphorus-containing epoxy resin.

[0011]

[Chemical 3] (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) may be mentioned.

The inorganic filler (C) used in the present invention is not particularly limited and includes talc, alumina, aluminum hydroxide, magnesium hydroxide and the like, and these can be used alone or in combination of two or more kinds. . The blending ratio of the inorganic filler is preferably 10 to 100% by weight based on the entire resin composition. If the blending amount is less than 10% 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 (D) curing agent used in the present invention can be used without particular limitation as long as it is a compound usually used for curing an epoxy resin. For example, as an amine curing system, dicyandiamide (DICY), aromatic Examples thereof include group diamines and the like, and examples of the phenol curing system include phenol novolac resins, cresol novolac resins, biphenol A type novolac resins, and these can be used alone or in combination of two or more kinds.

The (E) 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 build-up resin composition of the present invention has a high (A) weight average molecular weight of 10,000 or more.
A molecular weight resin , (B) a phosphorus-containing epoxy resin, (C) an inorganic filler, (D) a curing agent, and (E) a curing accelerator are essential components, but they are also required as long as they do not violate the object of the present invention. Accordingly, a nitrogen-containing compound that can serve as a flame retardant aid and a curing agent such as melamines, guanamines and melamine resins, guanamine resins can be added and blended.

To use the resin composition for buildup of the present invention in a resin film, the above-mentioned components (A) to (E) and other components are diluted with a suitable organic solvent such as methyl cellosolve to form a varnish. A resin film with a carrier can be obtained by a conventional method such as applying this to one side of a carrier sheet such as copper foil or polyester or polyimide and semi-curing. Further, 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 on a glass epoxy laminated board as a core.

[0017]

The present invention is characterized in that halogen is not used as a flame retardant method, and the (A) weight average molecular weight is 10,000 or more without generating toxic gas such as hydrogen bromide. By combining the high molecular weight resin , the phosphorus-containing epoxy resin (B), the inorganic filler (C), the curing agent (D) and the curing accelerator component (E), heat resistance and moisture resistance,
A resin composition having excellent corrosion resistance was obtained, and a resin film and a build-up type multilayer printed wiring board could be obtained by using the resin composition.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, "part" means "part 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 (manufactured by Sanko Chemical Co., Ltd., trade name) [10- (2,5-dihydroxyphenyl) -10
-Hydro-9-oxa-10-phosphaphenanthrene-10-oxide] 325 g was used as a reaction catalyst and 0.2 g of tetramethylammonium chloride was used as an aqueous solution, and the mixture was reacted at 170 ° C for 8 hours to give 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 (manufactured by Sanko Chemical Co., Ltd., trade name)
216 g of [9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide] was used as a reaction catalyst in an amount of 0.2 g of tetramethylammonium chloride as an aqueous solution and reacted at 170 ° C. for 5 hours to give a phosphorus content of 3 0.2% 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., epoxy equivalent 7900, resin solid content 40% by weight)
75 parts, 60 parts of phosphorus-containing epoxy resin synthesized in Synthesis Example 1 (resin solid content 75% by weight), dicyandiamide 1.3
Parts, 25 parts aluminum hydroxide, 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 (supra) of a bisphenol A type polymer epoxy resin having a weight average molecular weight of 50,000, the phosphorus-containing epoxy resin synthesized in Synthesis Example 2 (resin solid content 7
5 parts by weight) 60 parts, dicyandiamide 1.6 parts, aluminum hydroxide 25 parts, and 2-ethyl-4-methylimidazole 0.2 parts to which methylcellosolve was added to prepare an epoxy resin varnish having a resin solid content of 50% by weight. Prepared.

Comparative Example 1 75 parts of Epicoat 1256 (supra) 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, novolac type phenol resin BRG-558 (manufactured by Showa High Polymer Co., Ltd., hydroxyl equivalent 10)
6) 6.1 parts, 25 parts aluminum hydroxide, and 2-
Methyl cellosolve was added to 0.2 parts of ethyl-4-methylimidazole to prepare an epoxy resin varnish having a resin solid content of 50% by weight.

COMPARATIVE EXAMPLE 2 75 parts of Epicoat 1256 (supra) of bisphenol A type high molecular weight epoxy resin having a weight average molecular weight of 50,000, 35 parts of brominated epoxy resin (supra), 0.8 part of dicyandiamide, and 25 parts of aluminum hydroxide. , And 2-ethyl-4-methylimidazole (0.2 parts) were added with methyl cellosolve to prepare an epoxy resin varnish having a resin solid content of 50% by weight.

The epoxy resin varnishes obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were continuously applied to one surface of each copper foil,
A resin sheet with a carrier was manufactured by drying at a temperature of 150 ° C. The resin sheet with a carrier thus obtained was prepared on both sides of a laminate (Japanese Patent Application No. 11-153204) manufactured in advance by using a resin composition containing no halogen.
Heating and pressurizing at a temperature of ℃ for 90 minutes at a pressure of 40 MPa,
A build-up type multilayer printed wiring board having a thickness of 0.6 mm was obtained.

With respect to the obtained build-up type multilayer printed wiring board, flame retardancy, heat resistance and moisture resistance were measured and combustion gas analysis was carried out. The results are shown in Table 1. The build-up resin composition of the present invention, the build-up type multilayer printed wiring board using the resin film is comparable to those using the conventional brominated epoxy resin in any of the characteristics, and also long-term Regarding the peeling strength of deterioration, good results have been obtained because it does not contain bromine. on the other hand,
It was confirmed that hydrogen bromide, which is a problem during combustion, was not generated.

[0027]

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

* 2: Measured according to IEC-PB112.

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

* 4: Each sample shown in the table was floated on a solder bath at 260 ° C., and the presence or absence of swelling was observed and evaluated according to the following criteria. ◎: No swelling, ○: Some swelling, △
Sign: Most of them are swollen, and ×: All are swollen.

* 5: The sample was treated under condition A (boiling for 2 hours) or condition B (boiling for 4 hours) and then immersed in a solder bath at 260 ° C. for 30 seconds and observed for swelling. It evaluated by the standard of. ◎: No swelling, ○: Partially swollen, △: Mostly swollen, X: All swollen.

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

[0033]

As is apparent from the above description and Table 1, according to the present invention, halogen is not used as a flame retarding method, and toxic gas such as hydrogen bromide is generated during combustion. A resin composition having excellent heat resistance and humidity resistance without being provided is provided. As a result, 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.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP 2001-151990 (JP, A) JP 2000-239525 (JP, A) JP 11-279258 (JP, A) JP 11-340610 ( JP, A) JP-A-11-343398 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/00-59/72 C08L 63/00-63/10 C08L 101 / 00-101/16 H05K 3/46

Claims (6)

(57) [Claims] 1. An epoxy resin ( A) having a weight average molecular weight of 10,000 or more (provided that the epoxy equivalent is 500 or less).
( Excluding non-halogenated polyfunctional epoxy resin) , (B) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound represented by the following general formula: (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 represented by the following general formula. -Hydro-9-oxa-10-phosphaphenanthrene-10-oxide compound (Wherein, R is a hydrogen atom or a substituent other than halogen, and they may be the same or different from each other) as one of the reaction components, (C) an inorganic filler , (D) curing agent and (E) curing accelerator as essential components, the epoxy resin of (A), (A) ~
A resin composition for build-up, which is contained in a proportion of 5 to 70% by weight based on the total weight of (E) and is applied to build-up of a multilayer printed wiring board. 2. The components (A) to (E) are substantially non-halogen compounds, and the content of the impurity halogens thereof is 0.1% by weight or less for each of the components (A) to (E). The resin composition for buildup according to claim 1. 3. The resin composition for buildup according to claim 2, wherein the phosphorus content in the phosphorus-containing epoxy resin (B) is 0.2 to 8% by weight. 4. The (D) curing agent is dicyandiamide and its derivative, novolac type phenol resin, polyvinylphenol resin, organic acid hydrazide, diaminomaleonitrile and its derivative, melamine and its derivative, amine imide, polyamine, amine and acid anhydride. The resin composition for build-up according to claim 3, which is at least one curing agent selected from the group consisting of a resin, a polyamide and an imidazole. 5. A resin film with a carrier obtained by coating the build-up resin composition according to any one of claims 1 to 4 on one side of a copper foil or a carrier sheet. 6. A build-up type multilayer printed wiring board, which is obtained by successively laminating and molding the resin film according to claim 5 on a glass epoxy laminated board serving as a core.