JP2001049087A - Build-up type multi-layer printed wiring board, and resin composition and resin film used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having improved heat resistance, moisture resistance and corrosion resistance by blending a thermoplastic or thermosetting resin, an epoxy resin, a melamine and/or a benzoguanamine, 9,10-dihydro-p- oxa-10-phosphaphenanthrene-10-oxide, an inorganic filler, a curing agent and a curing promoter. SOLUTION: A composition for build-up which is applicable for build-up of a multi-layer printed wiring board is obtained by blending 5-70 wt.% of a thermoplastic or thermosetting resin having a weight average molecular weight of at least 10,000, an epoxy resin, a melamine and/or a benzoguanamine, 9,10- dihydro-p-oxa-10-phosphaphenanthrene-10-oxide (a derivative thereof) of the formula, 10-100 wt.% of an inorganic filler, a curing agent and a curing promoter. The composition, which has an improved heat resistance, or the like, does not emit any poisonous gas such as hydrogen bromide, or the like, when burned, and not contain a halogen for improving the flame resistance. In the formula, R is H, phenoxy or an alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, with the worldwide interest in environmental issues, in particular, safety to the human body, electricity and electric power have been increasing.
With respect to electronic devices, in addition to the conventional flame retardancy, there is an increasing demand for less harmfulness and higher safety. That is, it is demanded that electric and electronic devices not only hardly burn, but also generate less harmful gas and harmful dust. 2. Description of the Related Art Conventionally, a printed wiring board made of a glass-based epoxy resin on which electric / electronic components are mounted has generally been used as an epoxy resin as a brominated epoxy resin containing bromine as a flame retardant, for example, a tetrabromobisphenol A type epoxy resin. .

[0003] Although such a brominated epoxy resin has good flame retardancy, it generates harmful hydrogen halide (hydrogen bromide) gas during combustion, and its use is being suppressed.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to use a halogen-free flame-retarding method, generate no toxic gas such as hydrogen bromide during combustion, and provide excellent heat resistance, moisture resistance, and corrosion resistance. To provide a resin composition for build-up of a multilayer printed wiring board. 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 manufactured using the resin film. It is another object to provide a wiring board.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, they did not use a halogen-containing compound as a flame retardant in a resin composition for build-up, Or / and / or adding benzoguanamines together with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof to find that the above-mentioned object can be practically achieved. It has been completed.

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, (B) an epoxy resin, (C) a melamine or / and benzoguanamine, 9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof,

Embedded image (Wherein, R represents a hydrogen atom, a phenoxy group or an alkyl group) (E) an inorganic filler, (F) a curing agent and (G) a curing accelerator as essential components, and a thermoplastic resin (A) Alternatively, the thermosetting resin is added in an amount of 5 to 5% based on the total weight of (A) to (G).
A resin composition for build-up containing 70% by weight and applied to build-up of a multilayer printed wiring board, and the resin composition for build-up is provided on one side of a copper foil or a carrier sheet. A build-up type multilayer printed wiring board characterized by being formed by laminating a resin film with a carrier coated thereon and this resin film on a glass epoxy laminate board as a core sequentially.

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 the main chain or side chain, or those having a heat softening point temperature of 90 ° C. or higher are preferred but not limited in terms of improvement in heat resistance and moisture resistance (A). The compounding ratio of the components is 5 to 70% by weight based on the entire resin composition.

As the epoxy resin (B) used in the present invention, an epoxy resin having two or more epoxy groups in one molecule can be used. As the epoxy resin having two or more epoxy groups in one molecule, for example,
Bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, glycidyl ether type epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, etc., may be used alone or in combination of two or more. can do.

The melamines and / or benzoguanamines (C) used in the present invention include melamine, melamine cyanurate, benzoguanamine, acetoguanamine and the like, and melamine resins and benzoguanamine resins.
These can be used alone or in combination of two or more. Further, they can be used after being modified with a phenol resin or the like.

(D) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- used in the present invention
Oxide and its derivative are shown in Chemical formula 2, and particularly from the viewpoints of heat resistance, moisture resistance, flame retardancy, and chemical resistance, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxide (HCA) is preferred. HCA and its derivatives include, for example, HCA, HCA
-HQ, M-Acid-AH (trade name, manufactured by Sanko Co., Ltd.) and the like, and these can be used alone or in combination of two or more.

The inorganic filler (E) 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 as a mixture of two or more. . It is preferable that the mixing ratio of the inorganic filler is 10 to 100% by weight based on the whole resin composition. If the compounding 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.

As the curing agent as the component (F) used in the present invention, any compound can be used without particular limitation as long as it is a compound used for curing epoxy resins. For example, dicyandiamide (DICY) is used as an amine curing system. ), Aromatic diamines, and the like. Examples of phenol curing systems include phenol novolak resins, cresol novolak resins,
Biphenol A type novolak resins and the like can be mentioned, and these can be used alone or in combination of two or more. Further, (G) a curing accelerator usually used as a curing accelerator for epoxy resin,
Imidazole compounds such as 4-methylimidazole and 1-benzyl-2-methylimidazole; These curing accelerators can be used alone or in combination of two or more.

In order to use the resin composition for build-up of the present invention in a resin film, the above-mentioned components (A) to (G) 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.

[0016]

The present invention is characterized in that no halogen is used as a flame-retarding method, and the (A) weight average molecular weight is 10,000 or more without generating toxic gas such as hydrogen bromide during combustion. Thermoplastic resin or thermosetting resin, (B) epoxy resin, (C) melamines and / or benzoguanamines, (D) 9,10-dihydro-9
-Oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof, (E) an inorganic filler and (F)
Heat resistance by combining the curing agent and the (G) curing accelerator component,
A resin composition excellent in moisture resistance and corrosion resistance is obtained, and a resin film and a build-up type multilayer printed wiring board can be obtained by using the resin composition.

[0017]

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”.

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, epicoat 1001 of bisphenol A type epoxy resin (trade name, manufactured by Yuka Shell Co., epoxy equivalent 47
5) 35 parts, dicyandiamide 0.8 parts, melamine 5
Parts, HCA (trade name, manufactured by Sanko Co., Ltd.), 15 parts of aluminum hydroxide, and 25 parts of aluminum hydroxide, and 0.2 parts of 2-ethyl-4-methylimidazole were added with methyl cellosolve to prepare an epoxy resin varnish having a resin solid content of 50% by weight. Was prepared.

Example 2 Bisphenol A type epoxy resin having a weight average molecular weight of 50,000 Epicoat 1256 (described above) 75 parts, bisphenol A type epoxy resin epicoat 1001
(Supra) 28 parts, novolak type phenolic resin BRG-
558 (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106) 6.3
Part, melamine 5 parts, HCA (manufactured by Sankosha, trade name) 15
Parts, 25 parts of 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.

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.)
28 parts of epoxy equivalent 490), 6.1 parts of novolak type phenol resin (described above), 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 , And 0.2 parts of 2-ethyl-4-methylimidazole were added with methyl cellosolve to prepare an epoxy resin varnish having a resin solid content of 50% by weight.

Each of the epoxy resin varnishes obtained in Examples 1 and 2 and Comparative Examples 1 and 2 was continuously applied to one side 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 obtained 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.

[0024]

[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), the sample was immersed in a solder bath at 260 ° C. for 30 seconds, and the presence or absence of blister was observed. 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.

[0030]

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. The present invention provides a resin composition having excellent heat resistance and moisture resistance without being subjected to heat treatment. 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 (72) Inventor Katsura Ogawa 5-14-25 Ryoke, Kawaguchi-shi, Saitama F-term in Kawaguchi Plant of Toshiba Chemical Corporation (reference) 4J002 BE06W CB00W CC04Z CC05Z CC18Y CC19Y CD00W CD02X CD05X CD06X CF06W CF07W CF16W CG01W CH08W CH09W CK02W CL00W CM04W CN01W CN03W DE078 DE148 DJ048 ER029 EU119 EU186 EW137 FD018 FD149 FD159 GQ01 5E346 AA12 AA15 AA32 BB01 CC08 CC09 CC16 CC32 DD02 DD12 EE31 HGG18GG

Claims (3)

[Claims] 1. A thermoplastic resin or a thermosetting resin having a weight average molecular weight of 10,000 or more, (B) an epoxy resin, (C) melamines and / or benzoguanamines, and (D) represented by the following formula: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or a derivative thereof, (Wherein, R represents a hydrogen atom, a phenoxy group or an alkyl group) (E) an inorganic filler, (F) a curing agent and (G) a curing accelerator as essential components, and a thermoplastic resin (A) Alternatively, a thermosetting resin is contained in a ratio of 5 to 70% by weight based on the total weight of (A) to (G), and is applied to build up of a multilayer printed wiring board. Resin composition. 2. 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. 3. A build-up type multilayer printed wiring board, wherein the resin film according to claim 2 is successively laminated and formed on a glass epoxy laminate board as a core.