JP2975349B1 - Resin composition for glass epoxy copper clad laminate - Google Patents

Abstract

Abstract: [PROBLEMS] To use a halogen-free flame-retarding method without generating hydrogen bromide, which is a toxic gas at the time of combustion, without heat resistance,
Provided is a resin composition for a glass epoxy copper-clad laminate excellent in moisture resistance, moldability, and the like. SOLUTION: (A) an epoxy resin composed of a novolak type epoxy resin, (B) a nitrogen-containing novolak type phenol resin, (C) an addition type, reaction type or condensation type phosphate ester, (D) an inorganic filler and (E) a curing accelerator as an essential component, a phosphoric ester of (C) in an amount of 5 to 30% by weight based on the whole resin composition, and an epoxy resin as a novolak type epoxy resin of (A) It is a resin composition for a glass epoxy copper clad laminate using an epoxy resin varnish containing 51 to 100% by weight of the entire components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass epoxy copper having excellent heat resistance, moisture resistance, moldability, etc., without using halogen as a flame-retarding method, without generating hydrogen bromide which is a toxic gas during combustion. The present invention relates to a resin composition for a laminated laminate.

[0002]

2. Description of the Related Art In recent years, with the growing concern about global environmental issues and the safety of the human body, electric and electronic products have less harmful properties in addition to flame retardancy.
The demand for higher security is increasing. That is,
There is a demand for electric and electronic products not only to be difficult to burn, but also to reduce the generation of harmful gases and smoke. Conventionally, printed wiring boards on which electric and electronic components are mounted usually have a substrate made of glass epoxy, and the epoxy resin used therein is brominated epoxy containing bromine acting as a flame retardant, especially Derivatives centered on bromobisphenol A are commonly used.

[0003]

Although such a brominated epoxy resin has good flame retardancy, it generates harmful hydrogen halide (hydrogen bromide) gas during combustion.
Its use is being suppressed. Therefore, a composition in which a non-halogen flame retardant, for example, a nitrogen compound, a phosphorus compound, an inorganic compound, or the like is blended with an ordinary epoxy resin has been developed. However, these flame-retardant additives have a negative effect on the curing of the epoxy resin in a nitrogen-based composition, a phosphorus-based composition lowering the moisture resistance of a cured composition, and an inorganic compound impregnating a glass cloth with the composition. There is a problem such as a decrease in performance, and it is difficult to put it to practical use. The present invention has been made to solve the above-mentioned drawbacks, and does not use halogen as a flame-retardant method, does not generate hydrogen bromide which is a toxic gas at the time of combustion, and has heat resistance, moisture resistance, moldability, and the like. An object of the present invention is to provide a resin composition for a glass epoxy copper clad laminate excellent in water resistance.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the composition described below achieves the above object, and have completed the present invention. It is.

That is, the present invention provides a glass epoxy copper clad laminate in which a glass substrate is impregnated with an epoxy resin composition and a plurality of dried prepregs are laminated, and a copper foil is laminated on at least one side thereof and integrally molded. In the production of (A) an epoxy resin consisting of only a novolak type epoxy resin, (B) a nitrogen-containing novolak type phenol resin, (C) a phosphate, (D) an inorganic filler and (E) a curing accelerator. As an essential component, the entire resin composition [(A) + (B) +
(C) + (D) + (E)], wherein the phosphoric acid ester of (C) is contained at a ratio of 5 to 30% by weight. is there. Further, the above-mentioned resin composition for a copper-clad laminate, wherein the phosphate ester (C) is an addition type, a reaction type or a condensation type.

Hereinafter, the present invention will be described in detail.

The resin composition of the present invention comprises (A) an epoxy resin composed of a novolak type epoxy resin, (B) a nitrogen-containing novolak type phenol resin, (C) a phosphate, (D) an inorganic filler and (E) ) A curing accelerator is an essential component.

The novolak structure of the novolak type epoxy resin constituting the epoxy resin (A) used in the present invention includes phenol type, cresol type and bisphenol A type, and is widely used without any particular limitation. it can. These novolak epoxy resins
For example, they are commercially available from Toto Kasei Co., Ltd. and Dainippon Ink Industries, Ltd., and they can be used alone or in combination of two or more. The novolak-type epoxy resin used here preferably has a softening point of 40 ° C. to 150 ° C., and if it exceeds 150 ° C., the impregnation property is undesirably lowered. As for the mixing ratio, the total amount of the epoxy resin component ,
100% by weight of novolak type epoxy resin
You.

The (B) nitrogen-containing novolak type phenol resin used in the present invention can be obtained by subjecting a phenol, a formaldehyde, a melamine or a guanamine to a heating and dehydration condensation under an acidic catalyst. These nitrogen-modified phenolic resins are used as a curing agent for the epoxy resin. The hydroxyl equivalent and the nitrogen content are not particularly limited, but the nitrogen content is 1.0% by weight or more, particularly 3.0 to 10.0% by weight. It is preferable that if the nitrogen content is less than this, good flame retardancy cannot be obtained. The mixing ratio of the nitrogen-containing phenolic resin is adjusted so that the hydroxyl equivalent is 0.8 to 1.2 with respect to the epoxy equivalent, and it is desirable to add 10 to 50% by weight to the whole resin composition. When the compounding ratio is less than 10% by weight, flame retardancy and peeling strength cannot be obtained, and when it exceeds 50% by weight, moldability decreases. The optimum range is preferably 20 to 35% by weight.

The phosphate ester (C) used in the present invention is an additive phosphate ester such as triphenyl phosphate (TPP) or cresyl diphenyl phosphate (CDP), or a polyhydric phenol such as resorcinol, phenol or cresol. A reactive phosphate ester (RDP, trade name, manufactured by Ajinomoto Co., etc.) in which at least one hydroxyl group of the polyhydric phenol is left as a reaction free radical by esterification synthesis with a monohydric phenol; Condensed phosphate ester (PX-2) in which free hydroxyl groups in phosphate ester are consumed for esterification condensation
00, a trade name of Daihachi Chemical Industry Co., Ltd.), which can be widely used without any particular limitation.

The amount of the phosphoric acid ester is preferably 5 to 30% by weight based on the total amount of the components (A) to (E), that is, based on the whole resin composition. If it is less than 5% by weight, flame retardancy is not effective, and if it exceeds 30% by weight, heat resistance, moisture resistance and the like are undesirably reduced.

The (D) inorganic filler used in the resin composition of the present invention is for imparting an additional flame retardant, heat resistance and moisture resistance to the epoxy resin composition. These fillers include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide and the like, and can be used alone or in combination of two or more. It is desirable to mix the inorganic filler in a proportion of 10 to 50% by weight of the whole resin composition. If the compounding ratio is less than 10% by weight, sufficient flame retardancy, heat resistance and moisture resistance cannot be obtained, and if it exceeds 50% by weight, the resin viscosity increases, resulting in uneven coating of the base material, resulting in voids and poor thickness. Not preferred.

The (E) curing accelerator used in the resin composition of the present invention is one usually used as a curing accelerator for an epoxy resin, and includes 2-ethyl-4-methylimidazole,
Imidazole compounds such as 1-benzyl-2-methylimidazole are included. These curing accelerators can be used alone or in combination of two or more. The curing accelerator is
Used in a small amount sufficient to accelerate the curing of the epoxy resin.

The glass woven fabric, glass nonwoven fabric and copper foil used in the present invention can be used without any particular limitation as long as they are generally used for glass epoxy copper clad laminates.

The epoxy resin composition of the present invention described above is diluted with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, which is then formed into a porous glass substrate such as a glass nonwoven fabric or a glass woven fabric. A prepreg can be manufactured by a usual method of coating, impregnating, and heating. Also, a plurality of the prepregs may be laminated, and a copper foil may be laminated on one or both sides of the laminated structure, and then heated and pressed under a normal condition to obtain a glass epoxy copper clad laminate.

[0016]

The present invention is characterized in that no halogen is used as a flame-retardant method, and glass epoxy which is excellent in heat resistance, moisture resistance, moldability, etc. without generating hydrogen bromide which is a toxic gas at the time of combustion. A resin composition for a copper-clad laminate was obtained. A novolak-type epoxy resin cured with a nitrogen-containing phenol resin is particularly effective as a flame-retardant resin, and the use of this flame-retardant resin covers the weakness in the properties of the phosphate ester of the main flame-retardant material. On the other hand, the amount of the inorganic filler used can be kept in an appropriate range by the bond between the flame retardant resin and the phosphate ester.

[0017]

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

Example 1 Cresol novolak epoxy resin (epoxy equivalent 21
0, 270 parts of resin solid content 70%), 185 parts of nitrogen-modified phenol resin (resin solid content 60% by weight, nitrogen 4% by weight), 100 parts of aluminum hydroxide, PX of condensed phosphate ester
-200 (trade name, manufactured by Daiichi Kagaku Kogyo Co., Ltd.), 0.1 part of 2-ethyl-4-methylimidazole and propylene glycol monomethyl ether (hereinafter referred to as PGM) were added to give an epoxy resin having a resin solid content of 65% by weight. A resin varnish was prepared.

Example 2 Cresol novolak epoxy resin (epoxy equivalent 21
0, 270 parts of resin solid content 70%), 185 parts of nitrogen-modified phenol resin (resin solid content 60% by weight, nitrogen 4% by weight), 100 parts of aluminum hydroxide, RD of reactive phosphate ester
60 parts of P (manufactured by Ajinomoto Co., Inc.), 0.1 part of 2-ethyl-4-methylimidazole and PGM were added, and the resin solid content was increased.
A 65% by weight epoxy resin varnish was prepared.

Example 3 Cresol novolak epoxy resin (epoxy equivalent 21
0, 270 parts of resin solid content 70%), 185 parts of nitrogen-modified phenolic resin (resin solid content 60% by weight, nitrogen 4% by weight), 100 parts of aluminum hydroxide, CD of added phosphate ester
P (manufactured by Daihachi Chemical Industry Co., Ltd., trade name) 60 parts, 2-ethyl-4
0.1 parts of methylimidazole and PGM were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight.

Comparative Example 1 283 parts of a brominated epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 490, solid content: 75% by weight), cresol novolak epoxy resin (epoxy equivalent: 210, resin solid content)
34 parts of bisphenol A type novolak resin (manufactured by Dainippon Ink and Chemicals, hydroxyl value 118, solid content 70)
92 parts by weight), 200 parts of aluminum hydroxide, 2-ethyl-4
-PGM was added to a mixture consisting of 0.1 part of methyl imidazole to prepare an epoxy resin varnish having a resin solid content of 65% by weight.

Comparative Example 2 283 parts of a brominated epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 490, solid content: 75% by weight), cresol novolak epoxy resin (epoxy equivalent: 210, resin solid content)
70 parts by weight) 34 parts, dicyandiamide 7.5 parts, aluminum hydroxide 200 parts, 2-ethyl-4-methylimidazole 0.1
And dimethylformamide were added to prepare an epoxy resin varnish having a resin solid content of 65% by weight.

Each of the epoxy resin varnishes obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was continuously applied and impregnated on a glass woven fabric, and dried at a temperature of 160 ° C. to produce a prepreg. Eight pieces of the prepregs thus obtained are superimposed, copper foil having a thickness of 18 μm is superimposed on both sides of the laminate, and heated at 170 ° C. under a pressure of 40 kg / cm ² for 90 minutes.
Pressure was applied to obtain a 1.6 mm thick glass epoxy copper clad laminate.

The obtained copper-clad laminate was tested for flame retardancy, insulation resistance, peel strength, heat resistance, moisture resistance, and moldability. The results are shown in Table 1, and the effect of the present invention could be confirmed.

[0025]

[Table 1] * 1: Measured according to UL94 flame retardancy test. * 2: Measured according to IEC-PB112. * 3: Measured according to JIS-C-6481. * 4: Measured according to JIS-C-6481 after heat treatment at 170 ° C for 500 hours. * 5: The samples were floated on the solder bath at 260 ° C for each time shown in the table, and the presence or absence of blisters was observed and evaluated according to the following criteria. ◎: no swelling, ○: some swelling, Δ: most swelling, ×: all swelling. * 6: Treat the sample under condition A (boiled for 6 hours) or condition B (leaved in steam at 120 ° C, 2 atm for 7 hours), immerse it in a solder bath at 260 ° C for 30 seconds, and check for blistering. Were observed and evaluated according to the following criteria. ◎: no swelling, ○: partial swelling, △: most swelling, ×: all swelling.

[0026]

As is apparent from the above description and Table 1, the present invention is characterized in that no halogen is used as a flame-retardant method, and it does not generate hydrogen bromide which is a toxic gas during combustion. Thus, a resin composition for a glass epoxy copper clad laminate excellent in heat resistance, moisture resistance, moldability and the like can be obtained.

Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI // (C08K 13/02 3:00 5: 521) C08L 63:04 (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 63/04 C08K 5/521 C08G 59/62 B32B 27/38 C08J 5/54

Claims (4)

(57) [Claims] 1. A glass-epoxy copper-clad laminate is produced by laminating a plurality of prepregs impregnated and dried on a glass substrate with an epoxy resin composition and laminating a copper foil on at least one side thereof and integrally molding the prepregs. (A) an epoxy resin composed solely of a novolak type epoxy resin, (B) a nitrogen-containing novolak type phenol resin, (C) a phosphate ester, (D) an inorganic filler and E) a curing accelerator as an essential component, and the entire resin composition [(A) + (B) +
(C) + (D) + (E)], wherein the phosphoric ester of (C) is contained at a ratio of 5 to 30% by weight. 2. The resin composition for a glass epoxy copper clad laminate according to claim 1, wherein (C) the phosphate ester is an addition type. 3. The resin composition for a glass epoxy copper clad laminate according to claim 1, wherein (C) the phosphate ester is a reactive type. 4. The resin composition for a glass epoxy copper clad laminate according to claim 1, wherein (C) the phosphate ester is a condensation type.