JPH10120872A - Phenolic resin composition and phenolic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phenolic resin composition which can give a phenolic resin laminate having a good punching quality and flame retardancy by using a phenolic resin composition essentially consisting of a resol resin, specified novolac resin or of a resol resin, specified novolac resin and phosphorus flame retardant. SOLUTION: This composition essentially consists of a resol resin, benzoguanamine-modified novolac resin or of a resol resin, benzoguanamine- modified novolac resin and phosphorus flame retardant. The resol resin is obtained by reacting a phenol with an aldehyde in the presence of an alkali catalyst. The benzoguanamine-modified novolac resin is desirably one having a degree of modification with benzoguanamine of 10-30wt.%. This resin is used in amount of desirably 5-100 pts.wt. per 100 pts.wt. resol resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a phenolic resin composition and a phenolic resin laminate.

[0002]

2. Description of the Related Art A phenolic resin laminate is prepared by impregnating and drying a base material with a resol resin obtained by reacting phenols and aldehydes in the presence of an alkali catalyst to form a prepreg. It was heated and pressurized. A flame retardant is blended to make the phenolic resin laminate flame-retardant. Examples of the flame retardant include bromine-based flame retardants, phosphorus-based flame retardants, and nitrogen-based flame retardants. Among these, when punching after forming a laminate by a punching method, a phosphorus-based flame retardant is mainly blended, and a paper-based substrate is used as a substrate.

[0003]

However, when a large amount of a phosphorus-based flame retardant is incorporated, there is a disadvantage that the punching workability is deteriorated and the flame retardancy is also insufficient. An object of the present invention is to provide a phenolic resin composition capable of obtaining a phenolic resin laminate having good punching workability and flame retardancy and a phenolic resin laminate having good punching workability and flame retardancy. .

[0004]

SUMMARY OF THE INVENTION The present invention is a phenol resin composition containing a resole resin and a benzoguanamine-modified novolak resin as essential components.

Further, the present invention is a phenol resin composition containing a resole resin, a benzoguanamine-modified novolak resin and a phosphorus-based flame retardant as essential components.

Further, the present invention is a phenolic resin laminate obtained by laminating a prepreg impregnated and dried with a varnish of the phenolic resin composition on a substrate, and applying heat and pressure.

[0007]

DETAILED DESCRIPTION OF THE INVENTION A resol resin is obtained by reacting a phenol and an aldehyde in the presence of an alkali catalyst such as ammonia. As phenols, phenol, meta-cresol, para-cresol, ortho-cresol, isopropylphenol, para-tert-butylphenol, nonylphenol, bisphenol A and the like are used. In order to impart flexibility to the laminate, the resol resin is preferably modified with a drying oil. A phenol and a drying oil are reacted in the presence of an acid catalyst, and then an aldehyde is reacted in the presence of an alkali catalyst to obtain a drying oil-modified resole resin. As the drying oil, tung oil, linseed oil, dehydrated castor oil, deer oil, etc. are used. Aldehydes include, but are not particularly limited to, formaldehyde, paraformaldehyde, acetaldehyde, paraacetaldehyde, butyraldehyde, octylaldehyde, benzaldehyde, and the like. Generally, formaldehyde or paraformaldehyde is used.

As the benzoguanamine-modified novolak resin, a commercially available product can be used, and the benzoguanamine-modified novolak resin has a benzoguanamine modification ratio of 1
Those having 0 to 30% by weight are preferred. If the benzoguanamine modification rate is less than 10% by weight, no effect is observed,
If the content is more than 10% by weight, the punchability tends to be poor. From such a viewpoint, the benzoguanamine modification rate is 2
0 wt% is most preferred. The benzoguanamine-modified novolak resin reacts with the resole resin and contributes to flame retardancy. For this reason, it is preferable to mix in a range of 5 to 100 parts by weight with respect to 100 parts by weight of the resole resin. If the compounding amount is less than 5 parts by weight with respect to 100 parts by weight of the resole resin, the effect of imparting flame retardancy is insufficient, and
If it exceeds 0 parts by weight, the punching workability tends to deteriorate. From this, with respect to 100 parts by weight of the resole resin,
It is more preferable to mix in the range of 15 to 50 parts by weight.

Phosphorus flame retardants include phosphate esters,
Halogen-containing phosphate esters, condensed phosphate esters, polyphosphate esters, and the like are used. Among them, it is preferable to use triphenyl phosphate because it is inexpensive. The phosphorus-based flame retardant is preferably blended in an amount of 10 to 100 parts by weight based on 100 parts by weight of the resole resin. If the compounding amount is less than 10 parts by weight with respect to 100 parts by weight of the resole resin, the effect of compounding is small. .

The phenolic resin composition of the present invention contains, in addition to phosphorus-based flame retardants, other flame retardants, for example, inorganic filler-based flame retardants such as aluminum hydroxide, and bromine-based flame retardants such as brominated epoxy resins. Flame retardants and nitrogen-based flame retardants such as melamine may be added in a range of up to 30 parts by weight based on 100 parts by weight of the total composition. When a flame retardant other than these phosphorus-based flame retardants is blended, the flame retardancy can be further enhanced with a small amount due to synergistic action, and the blended amount of the flame retardant can be reduced. If the amount of the flame retardant other than the phosphorus-based flame retardant exceeds 30 parts by weight, the punching workability and the heat resistance tend to deteriorate.

The phenolic resin composition of the present invention is dissolved in a solvent and impregnated as a varnish onto a substrate. As a solvent for forming a varnish, toluene, methanol, methyl ethyl ketone, 2-methoxyethanol, acetone, styrene and the like are used.

As the substrate impregnated with the varnish, a paper-based substrate is preferably used from the viewpoint of punching workability. Kraft paper obtained by making kraft pulp is mainly used as a paper base material.Cotton linter paper, mixed paper of linter and kraft pulp, glass paper, glass nonwoven fabric, and mixture of glass fiber and paper fiber are used. Papermaking can also be used. It is preferable that a water-soluble phenol resin is previously adhered to these substrates.

The varnish is impregnated into a substrate and dried to form a prepreg. A predetermined number of the obtained prepregs are laminated, and a copper foil is laminated thereon, at a temperature of 150 to 180 ° C. and a pressure of 9 to 20.
Heat and pressurize at MPa to make a phenolic resin laminate.

[0014]

【Example】

Example 1 200 g of tung oil, 334 g of phenol, and 0.2 g of paratoluenesulfonic acid were charged into a reaction vessel and reacted at 90 ° C. for 1 hour. Then, 200 g of paraformaldehyde and 30 g of aqueous ammonia were added and reacted at 75 ° C. for 2 hours. A tung oil-modified resole resin having a tung oil modification rate of 35% by weight was obtained. 100 parts of tung oil-modified resol resin (parts by weight, the same applies hereinafter), benzoguanamine-modified novolak resin having a benzoguanamine modification rate of 20% by weight (manufactured by Dainippon Ink and Chemicals, Inc.
10 parts of A7051 (trade name) and 50 parts of triphenyl phosphate were dissolved in a mixed solvent of equivalent amounts of methanol and toluene to prepare a varnish having a resin content of 50% by weight. Water-soluble phenolic resin (VP-03N (trade name) manufactured by Hitachi Chemical Co., Ltd.) was previously applied to kraft paper having a thickness of 0.2 mm and a basis weight of 125 g / m ² , and the adhesion amount was 12% by weight. Then, the varnish was impregnated with the varnish so that the total resin adhesion amount after drying was 50% by weight, and dried to obtain a prepreg. The obtained eight prepregs were stacked, and the thickness of the copper foil was 35 μm on one side.
A copper foil with an adhesive was overlaid so that the adhesive layer was on the prepreg side, and heated and pressed at a temperature of 170 ° C. and a pressure of 15 MPa for 90 minutes to obtain a single-sided copper-clad laminate having a thickness of 1.6 mm.

Comparative Example A single-sided copper-clad laminate having a thickness of 1.6 mm was obtained in the same manner as in Example 1 except that no benzoguanamine-modified novolak resin was added.

With respect to the single-sided copper-clad laminate obtained above,
Flame retardancy and punching workability were examined. Table 1 shows the results.

The test method was as shown below. Flame retardancy From the obtained single-sided copper-clad laminate, a copper foil was entirely etched to cut out a 127 mm x 12.7 mm test piece.
The test piece was held so that the long side was vertical, and the flame contact was repeated twice for 10 seconds from below with a burner, and the time until the flame was extinguished was measured. In Table 1, the term "after treatment" means that the test piece was examined after being kept in an oven at 125C for 24 hours. The flame retardancy test was performed on five test pieces, and the average value and the range of the measured values (in parentheses) were shown. Punching workability Punch diameter 1.0-1.2m by changing surface temperature of test piece
m, a pitch between holes of 2.54 mm, and punched one by one using a 24-hole test mold. Then, the periphery of the hole was visually observed, and the state was indicated by a symbol. The meanings of the symbols are as follows. ：: peeling, no whitening Δ: peeling, slight whitening ×: peeling, large whitening

[0018]

[Table 1] 試 料 Sample Example 1 Comparative Example ───────燃 Flame retardancy Normal (seconds) 1.5 (0-3) 2.8 (0-5) Difficult Flammability After treatment (seconds) 2.5 (0 to 6) 3.2 (0 to 10) Punching workability 20 ° C △ ～ × △ ～ × Punching workability 40 ℃ ○ 〜 △ ○ 〜 △ Punching workability 60 ℃ ○ ○ 〜 △ Punching workability 80 ℃ ○ 〜 △ ○ 〜 △ Punching workability 100 ℃ ○ 〜 △ △ 〜 × ━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━

[0019]

By using the phenolic resin composition according to the present invention, a phenolic resin laminate excellent in both flame retardancy and punching workability can be obtained.

Claims (3)

[Claims] 1. A phenol resin composition comprising a resole resin and a benzoguanamine-modified novolak resin as essential components. 2. A phenol resin composition comprising a resole resin, a phosphorus-based flame retardant and a benzoguanamine-modified novolak resin as essential components. 3. A phenolic resin laminate obtained by laminating a prepreg obtained by impregnating and drying a varnish of the phenolic resin composition according to claim 1 on a substrate and heating and pressing the prepreg.