JP3315082B2 - Flame-retardant resin composition, prepreg and laminate using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a prepreg and a laminate having excellent flame retardancy without using a halogen-based flame retardant.

[0002] Thermosetting resins represented by epoxy resins are widely used for electric and electronic equipment parts due to their excellent characteristics, and are provided with flame retardancy to ensure fire safety. There are many. Conventionally, these resins have generally used a halogen-containing compound such as a brominated epoxy resin. Although these halogen-containing compounds have high flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide by thermal decomposition, but also have high toxicity when decomposed in the presence of oxygen. May form bromodibenzofuran and polydibromobenzooxin. Further, disposal of aging waste material containing bromine is extremely difficult. For these reasons, phosphorus compounds and nitrogen compounds have been studied as flame retardants instead of bromine-containing flame retardants.

[0003] As described above, flame retardancy can be realized by a phosphorus compound and a nitrogen compound. The mechanism is that the nitrogen compound promotes the decomposition of the phosphorus compound and the production of polyphosphoric acid by thermal condensation, and the polyphosphoric acid forms a film on the surface of the epoxy resin, which has an insulating effect and an oxygen blocking effect, and as a result, combustion It is to prevent. It is a well-known fact that triazine-modified novolak has high flame retardancy and is an excellent compound as a nitrogen compound used for flame retardation.

When a triazine-modified novolak is used as a curing agent for an epoxy, a triazine-modified novolak having a high nitrogen content has a large hydroxyl equivalent and a small curing shrinkage. Has the advantage of improving However, when the nitrogen content is increased, there is a disadvantage that moisture absorption becomes easy, and thus heat resistance to moisture absorption solder deteriorates.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and has been developed by using a triazine-modified novolak and a phenol aralkyl resin or a naphthalene aralkyl resin in combination to improve adhesion. A resin that has excellent heat resistance to moisture absorption soldering, and that does not exhibit flame retardancy without using halogen due to the interaction of nitrogen and phosphorus by using a phosphorus atom-containing compound in combination, and has high flame retardancy It is intended to provide a composition, a prepreg and a laminate obtained from the prepreg.

[0006]

The present invention provides (A) a non-halogenated epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent comprising a triazine-modified novolak, A curing agent comprising a phenol aralkyl resin represented by the formula (1) and / or a naphthalene aralkyl resin represented by the general formula (2);

Embedded image (D) A flame-retardant resin composition comprising, as an essential component, a phosphorus atom-containing compound containing no halogen atom in the molecule. And the present invention is a prepreg characterized in that the base material is impregnated with the flame-retardant resin composition, and further characterized in that one or more prepregs described above are stacked and heated and pressed. Flame-resistant laminate or copper-clad laminate.

[0007] As described above, triazine-modified novolak is useful as a nitrogen-based flame retardant for epoxy resins. When a triazine-modified novolak is used as a curing agent for an epoxy resin, a triazine-modified novolak having a high nitrogen content has a large hydroxyl equivalent and a small curing shrinkage, so that when used as a varnish for a laminate, the adhesion is good. Become. However, when the nitrogen content is increased, there is a disadvantage that moisture absorption becomes easy, and thus heat resistance to moisture absorption solder deteriorates.

The phenol aralkyl resin represented by the above general formula (1) and / or the naphthalene aralkyl resin represented by the general formula (2) have a large hydroxyl equivalent, so that the curing shrinkage is small, and the benzene ring or naphthalene The ring has the characteristics that it has a low water absorption due to its hydrophobicity, and it is difficult to burn because it is a resin with a high residual carbon ratio. Therefore, the combined use of the aralkyl-based resin and the triazine-modified novolak having a high nitrogen content satisfies the adhesive force and the heat resistance of the moisture-absorbing solder simultaneously and increases the flame resistance. In the present invention, a triazine-modified novolak, a phenol aralkyl resin and / or a naphthalene aralkyl resin are used as a curing agent for an epoxy resin, and furthermore, by using a phosphorus component in combination, the interaction between nitrogen and phosphorus does not use a halide to provide flame retardancy. The main point of the technology is to express the nature.

The component (A) used in the present invention includes bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A novolak epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, and tetrakis (glycidyloxyphenyl).
Ethane and the like can be mentioned, but it is not limited to these, and several kinds may be used at the same time.

The component (B) used in the present invention is a curing agent composed of a triazine-modified novolak, and is represented by the following general formula (3). Triazine-modified novolaks having a nitrogen content of 10% or more are desirable because a low nitrogen content has a small effect on flame retardancy.

Embedded image

The component (D) used in the present invention includes trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and crexylenyl phosphate. Zirdiphenyl phosphate,
Phosphoric acid esters such as xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate and resorcinol diphenyl phosphate, and condensed phosphoric acid esters such as dialkylhydroxymethyl phosphonate are exemplified. However, the present invention is not limited to this. In order not to impair the excellent properties of the epoxy resin, those which react with the epoxy resin are desirable, and in particular, 9,10-dihydro-
9-oxa-10-phosphaphenanthrene-10-oxide is preferred.

The flame-retardant resin composition of the present invention comprises the above-mentioned non-halogenated epoxy resin, a curing agent comprising a triazine-modified novolak as a curing agent, and a phenol aralkyl resin and / or a naphthalene aralkyl resin. Although containing a phosphorus atom-containing compound containing no halogen atom in the molecule as an essential component as a flame retardant, other curing agents within a range not contrary to the object of the present invention,
A curing accelerator, a coupling agent, and other components may be added.

Although the flame-retardant resin composition of the present invention is used in various forms, a solvent is usually used when impregnating the substrate. It is desirable that the solvent used has good solubility in the composition, but a poor solvent may be used as long as it does not adversely affect the composition.

The varnish obtained by dissolving the flame-retardant resin composition of the present invention in a solvent is applied and impregnated on a substrate such as glass woven fabric, glass non-woven fabric, or woven fabric or non-woven fabric containing a component other than glass. Prepreg can be obtained by drying at 80 to 200 ° C. Such a prepreg is used for producing a laminate or a copper-clad laminate by heating and pressing. The flame-retardant resin composition of the present invention is a thermosetting resin composition having high flame retardancy even without containing a halogen compound, and is particularly preferably used for a laminated board for printed wiring boards and the like. It is.

[0015]

(Example 1) Phenol novolak epoxy resin (Epiclon N-77 manufactured by Dainippon Ink and Chemicals, Inc.)
0) 100 parts by weight, 47 parts by weight of bisphenol F type epoxy resin (Epototo YDF-2004 manufactured by Toto Kasei Co., Ltd.), 19 parts by weight of phenol aralkyl resin (Mirex XLC-LL manufactured by Mitsui Chemicals, Inc.), nitrogen-containing phenol novolak (LA-705 manufactured by Dainippon Ink and Chemicals, Inc.)
4) Methyl cellosolve was added to 38 parts by weight and 35 parts by weight of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA manufactured by Sanko Chemical Co., Ltd.), and the non-volatile content was 60 parts by weight. % Was prepared. At this time, the phosphorus component was 2.1 parts by weight and the nitrogen component was 1.9 parts by weight based on 100 parts by weight of the epoxy resin, the phosphorus compound and the curing agent in total. Using this varnish, a glass woven cloth (0.18 mm thick, Nitto Boseki Co., Ltd.)
80 parts by weight of varnish solids into 100 parts by weight of varnish and dried in a dryer oven at 150 ° C. for 5 minutes to obtain a resin content of 4%.
A prepreg of 4.4% by weight was produced. Six pieces of the above prepregs are stacked, and an electrolytic copper foil having a thickness of 35 μm is stacked on the upper and lower sides, and heated and pressed at a pressure of 40 kgf / cm ² and a temperature of 190 ° C. for 120 minutes to form a double-sided copper-clad laminate having a thickness of 1.2 mm. I got a board.

(Examples 2 to 4 and Comparative Examples 1 and 2)
, A double-sided copper-clad laminate was produced in the same manner as in Example 1 except for the above formulation.

The resulting copper-clad laminate has flame retardancy,
Solder heat resistance and peel strength were measured. Flame retardancy is U
It was evaluated by the vertical method according to the L-94 standard. Solder heat resistance and peel strength were measured in accordance with JIS C 6481. Solder heat resistance was determined by examining the appearance after solder immersion in a solder bath at 260 ° C for 120 seconds after performing a moisture absorption treatment for 2 hours after boiling. Examined. Table 1 shows the evaluation results. Each of the copper-clad laminates shown in Examples has excellent flame resistance and solder heat resistance.

[0018]

[Table 1]

Notes to Table 1 (1) Epicron N-7 manufactured by Dainippon Ink and Chemicals, Inc.
70 Epoxy equivalent = 190 (2) Epicron N-6 manufactured by Dainippon Ink and Chemicals, Inc.
90 Epoxy equivalent = 210 (3) Epototo YDF-2004 manufactured by Toto Kasei Co., Ltd.
Epoxy equivalent = 940 (4) MILEX XLC-LL manufactured by Mitsui Chemicals, Inc. Hydroxyl equivalent = 175 (5) SN-170 manufactured by Nippon Steel Chemical Co., Ltd.
185 (6) LA-7054 manufactured by Dainippon Ink and Chemicals, Inc. Hydroxyl equivalent = 125 Nitrogen content = 12% (7) 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Phosphorus content Rate = 1
4.3%

[0020]

The present invention has a high level of flame retardancy without adding a halogen compound, and also has excellent properties such as solder heat resistance. Accordingly, the present invention provides a novel thermosetting resin composition as a non-halogen material required in the future, and a prepreg and a laminate using the same.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 63/00-63/10 B32B 15/08 C08L 61/06-61/10 C08J 5/24

Claims (4)

(57) [Claims] 1. A non-halogenated epoxy resin having two or more epoxy groups in one molecule, (B) a curing agent comprising a triazine-modified novolak, and (C) a curing agent represented by the general formula (1). A curing agent comprising a phenol aralkyl resin and / or a naphthalene aralkyl resin represented by the general formula (2), and (D) A flame-retardant resin composition comprising, as an essential component, a phosphorus atom-containing compound containing no halogen atom in the molecule. 2. The flame-retardant resin composition according to claim 1, which contains 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as the phosphorus atom-containing compound as the component (D). 3. A prepreg obtained by impregnating a substrate with the flame-retardant resin composition according to claim 1. 4. A flame-retardant laminate or a copper-clad laminate, wherein at least one prepreg according to claim 3 is overlaid and heated and pressed.