JP3183748B2 - Method for producing flame-retardant laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a flame-retardant laminate excellent in low-temperature punching workability.

[0002]

2. Description of the Related Art Paper-phenol resin laminates are punched or contoured by punching with a die. In recent years, punching has been performed at room temperature in order to reduce the dimensional change of printed wiring boards. The phenol resin alone is not flexible and has poor punching workability, so the phenol resin is modified to be flexible. In order to achieve flame retardancy, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an inorganic flame retardant represented by antimony trioxide, and an epoxy group-containing flame retardant are appropriately blended.

[0003] In order to make the phenolic resin flexible, the phenolic resin is generally modified with a highly reactive tung oil containing eryostearic acid as a main component. However, tung oil is subject to severe price fluctuations and difficulties in obtaining it in many cases, and there are difficulties in supply stability, so linoleic acid and linolenic are easy to obtain, inexpensive to supply, and both prices are stable. Use of a drying oil or a semi-drying oil containing an acid as a main component has been studied. Such vegetable oils include linseed oil, soybean oil, safflower oil and the like, but have poor reactivity with phenols. Therefore, it has been proposed to react with phenols under severe reaction conditions such as using a large amount of a Lewis acid catalyst (see JP-A-55-3903 and JP-A-55-108414).

[0004]

However, when a large amount of Lewis acid catalyst is used, hydrolysis of vegetable oil occurs at the same time and low molecular weight components increase. For this reason, when a laminated board is used, these low molecular weight components and unreacted vegetable oil ooze out on the surface, and the use of a large amount of catalyst causes a problem that the electrical properties of the laminated board are deteriorated. It is not possible to obtain a laminate that can withstand the heat. That is, when made into a laminate, the crosslinking density does not increase, the curing degree is insufficient,
The interlayer adhesion is weak, and bulges occur during punching. Further, the solvent resistance was low, and there was a problem in practical use.

The present invention solves the above-mentioned problems, and uses a drying oil or a semi-drying oil containing linoleic acid or linolenic acid as a main component as a modifier for a phenol resin, and is inexpensive and excellent in low-temperature punching workability. It is an object of the present invention to provide a method for manufacturing a flammable laminate.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a drying oil or semi-drying oil containing linoleic acid and / or linolenic acid as a main component, and using a phenol as a catalyst with a super strong acid such as perfluoroalkanesulfonic acid as a catalyst. And a vegetable oil-modified phenolic resin obtained by resolving the same,
A method for producing a flame-retardant laminate, characterized in that a predetermined number of prepregs obtained by impregnating and drying a fibrous base material with a resin varnish containing an epoxy-based reactive flame retardant as an essential component are heated and pressed. is there.

[0007] Vegetable oils containing linoleic acid and linolenic acid as main components used in the present invention include linseed oil, safflower oil, soybean oil, sesame oil, eno oil, asami oil, rapeseed oil, cottonseed oil, dehydrated castor oil and the like. In particular, linseed oil having a high degree of unsaturation, a low price, and a stable supply is preferred.

[0008] Phenols include phenol, ortho-cresol, meta-cresol, para-cresol, xylenol, catechol, resorcinol, hydroquinone,
Octyl phenol, tert-butyl phenol, nonyl phenol, bisphenol-A and the like can be mentioned.

The perfluoroalkanesulfonic acid used as a catalyst for the reaction between vegetable oil and phenols includes trifluoromethanesulfonic acid, pentafluoromethanesulfonic acid, heptafluoromethanesulfonic acid, nonafluoromethanesulfonic acid, undecafluoromethanesulfonic acid. Acids and the like. Particularly, trifluoromethanesulfonic acid is preferred.

The mixing ratio of vegetable oil to phenols is not particularly limited, but vegetable oil: phenols = 2: 8 to 6: 4, preferably 3: 7 to 4: 6, from the characteristics of the laminated board.
When the blending ratio of the vegetable oil is larger than 6: 4, the curability of the laminate decreases, and defects such as sticky surfaces appear.
On the other hand, when the ratio is smaller than 2: 8, the low-temperature punching workability of the laminate cannot be satisfied.

The amount of the catalyst to be added is not particularly limited, but is preferably 3 to 0.001 part by weight, particularly preferably 0.01 to 0.05 part by weight, per 100 parts by weight of the vegetable oil. If the amount is more than 3 parts by weight, the electrical properties of the laminated board deteriorate, and
If the amount is less than 01 parts by weight, the reaction will be slow and the industrial productivity will decrease.

The reaction between the vegetable oil and the phenol can be carried out in the absence of a solvent or in a solvent. However, considering the following reaction with formaldehyde, the reaction is preferably carried out without a solvent. The reaction temperature is preferably from 50 to 250C, particularly preferably 100C or lower. When the temperature is 100 ° C. or higher, a hydrolysis reaction frequently occurs, and a low molecular weight is likely to occur.

In order to improve the compatibility between the vegetable oil and the phenol resin, the phenol and the aromatic hydrocarbon formaldehyde resin may be reacted in the presence of an acidic catalyst before the reaction between the vegetable oil and the phenol.

Examples of the acidic catalyst include p-toluenesulfonic acid, benzenesulfonic acid and the like, and a perfluoroalkanesulfonic acid used in the reaction with vegetable oil, a so-called super strong acid, is preferred. Examples of the aromatic hydrocarbon formaldehyde resin include a xylene resin and a toluene resin.

After the reaction between the vegetable oil and the phenols is completed, phenol is optionally added, and formaldehyde and a basic catalyst are added to carry out a usual resolving reaction to synthesize a resin for a laminate.

An epoxy resin-based reactive flame retardant is blended with the modified phenolic resin thus synthesized. Examples of the epoxy resin-based reactive flame retardant include a reaction product of tetrabromobisphenol-A with epichlorohydrin, an epichlorohydrin adduct of polybromophenols, and a brominated novolak epoxy resin.

These bromine-containing epoxy flame retardants may be used in combination with other flame retardants, for example, inorganic flame retardants such as phosphorus flame retardants, nitrogen flame retardants and antimony trioxide. The varnish thus obtained is impregnated into a paper substrate and dried by heating to prepare a prepreg. A predetermined number of these sheets are stacked, copper foil with an adhesive is stacked, and pressurized and heated at a predetermined pressure and temperature for a predetermined time to obtain a flame-retardant copper-clad laminate.

When a drying oil or a semidrying oil containing a conjugated double bond in a molecule as a main component is reacted with a drying oil or a semidrying oil to which a phenol is added, linoleic acid or linoleic acid added with a phenol is added. Linolenic acid and a fatty acid containing a conjugated double bond in the molecule, such as linoleic acid or linolenic acid having a conjugated double bond, are bonded via phenols to increase the molecular weight, thereby further improving the heat resistance of the resin. .
Examples of the drying oil or semi-drying oil mainly containing a fatty acid containing a conjugated double bond in the molecule include tung oil and isomerized linseed oil. In this case, the ratio of the drying oil or semi-dry oil containing linoleic acid or linolenic acid as a main component and the drying oil or semi-dry oil containing a fatty acid containing a conjugated double bond in the molecule as a main component is expressed by weight. The former is 95-30, while the latter is 5-30
It is preferably 70.

[0019]

[Function] Linseic acid and linolenic acid as a main component can add phenols sufficiently, but it is difficult to polymerize linseed oil and other vegetable oils. Isomerized linseed oil in which the double bond is conjugated, polymerization of the isomerized linseed oil extremely easily occurs under a catalyst such as super strong acid. In other words, if a special catalyst is selected, linoleic acid and vegetable oils containing linolenic acid as a main component can be reacted with phenols while suppressing the reduction of molecular weight. Further, the polymerization of isomerized linseed oil is accelerated, and a phenol adduct of vegetable oil is obtained.

[0020]

【Example】

Example 1 200 g of linseed oil, 200 g of phenol, and 0.3 g of trifluoromethanesulfonic acid were charged into a 21-neck flask equipped with a thermometer and a condenser, and reacted at 80 ° C. for 3 hours. After completion of the reaction, phenol 180 g, paraform 25
5 g, 80 g of methanol and 38 g of aqueous ammonia were added, and further reacted at 80 ° C.

When the gelation time at 160 ° C. became 6 minutes, the mixture was heated under reduced pressure and dehydrated and concentrated. When the gelation time became 3 minutes, the reaction was terminated.
g of methanol and 200 g of methanol, and the reaction product of tetrabromobisphenol-A with epichlorohydrin (YD
B-400 150 g of Toto Kasei Co., Ltd. and 150 g of triphenyl phosphate were dissolved with stirring to form a varnish.

Example 2 In a 21 three-necked flask equipped with a thermometer and a cooling tube, 50 g of xylene resin (trade name of Nicanol-H, Mitsubishi Gas Chemical Co., Ltd.), 250 g of m, p-cresol, 1.0 g of fluorosulfonic acid And reacted at 90 ° C. for 1 hour. Further, 200 g of linseed oil was added thereto.
Allowed to react for hours. Next, 100 g of phenol, 177 g of paraform, 60 g of methanol, and 21.6 of aqueous ammonia.
g was added and reacted at 80 ° C.

When the gelation time at 160 ° C. became 6 minutes, the mixture was heated under reduced pressure and dehydrated and concentrated. When the gelation time became 3 minutes, the reaction was terminated.
g of methanol and 200 g of methanol, and a reaction product of tetrabromobisphenol-A with epichlorohydrin (ES
B-400 150 g of Sumitomo Chemical Co., Ltd. and 150 g of triphenyl phosphate were dissolved with stirring to form a varnish.

Example 3 200 g of phenol, 50 g of xylene resin (trade name of Nicanol-H, Mitsubishi Gas Chemical Co., Ltd.), and 1.0 g of trifluoromethanesulfonic acid were placed in a 21-neck flask equipped with a thermometer and a cooling tube. The reaction was carried out at 100 ° C. for 1 hour, and 200 g of soybean oil was further added, followed by a reaction at the same temperature for 5 hours. Next, 180 g of phenol, 255 g of paraform, 80 g of methanol and 38 g of aqueous ammonia were added and reacted at 80 ° C.

When the gelation time at 160 ° C. became 6 minutes, the mixture was heated under reduced pressure and dehydrated and concentrated. When the gelation time became 3 minutes, the reaction was terminated.
g of methanol and 200 g of methanol, and the reaction product of tetrabromobisphenol-A with epichlorohydrin (YD
B-400 100 g of Tohto Kasei Co., Ltd., epichlorohydrin adduct of a polybromophenol (BR)
-200 50 g of Nippon Kayaku Co., Ltd.) and 150 g of triphenyl phosphate were dissolved with stirring to form a varnish.

Example 4 In a 21 three-necked flask equipped with a thermometer and a cooling tube, 80 g of xylene resin (trade name of Nicanol-H, Mitsubishi Gas Chemical Co., Ltd.), 250 g of m, p-cresol, and 0.1 g of trifluoromethanesulfonic acid were added. 5 g was charged and reacted at 80 ° C. for 1 hour.
The reaction was performed at 0 ° C. for 2 hours. 50 g of tung oil was added to the reaction solution and reacted at the same temperature for 1 hour. After completion of the reaction, 170 g of phenol, 190 g of paraform, and 80 g of methanol
g and 27 g of aqueous ammonia were added and reacted at 80 ° C.

When the gelation time at 160 ° C. became 6 minutes, the mixture was heated under reduced pressure and dehydrated and concentrated. When the gelation time became 3 minutes, the reaction was terminated.
g, methanol 200 g, and brominated novolak type epoxy resin (BREN Nippon Kayaku Co., Ltd.) 2
00 g and 150 g of triphenyl phosphate were dissolved with stirring to form a varnish.

Comparative Example 1 A 2-liter three-necked flask equipped with a thermometer and a condenser was charged with 50 g of xylene resin (trade name of Nicanol-H, Mitsubishi Gas Chemical Co., Ltd.), 250 g of m, p-cresol, and trifluoromethanesulfonic acid 1 0.0 g, and reacted at 90 ° C. for 1 hour. Further, 200 g of linseed oil was added and reacted at the same temperature for 2 hours. Next, 100 g of phenol,
177 g of paraform, 60 g of methanol and 21.6 g of aqueous ammonia were added and reacted at 80 ° C.

When the gelation time at 160 ° C. became 6 minutes, the mixture was heated under reduced pressure and concentrated by dehydration. When the gelation time became 3 minutes, the reaction was terminated.
g, methanol 200 g, and tetrabromobisphenol-A (known as an addition-type brominated flame retardant)
135 g and 50 g of triphenyl phosphate were added to form a varnish.

Comparative Example 2 50 g of xylene resin (trade name of Nicanol-H, Mitsubishi Gas Chemical Co., Ltd.), 250 g of m, p-cresol, and trifluoromethanesulfonic acid 1 were placed in a two-liter three-necked flask equipped with a thermometer and a condenser. Then, the mixture was reacted at 90 ° C. for 1 hour, and further, 200 g of linseed oil was added and reacted at the same temperature for 2 hours. Next, 100 g of phenol,
177 g of paraform, 60 g of methanol and 21.6 g of aqueous ammonia were added and reacted at 80 ° C.

When the gelation time at 160 ° C. became 6 minutes, the mixture was heated under reduced pressure and concentrated by dehydration. When the gelation time became 3 minutes, the reaction was terminated.
g, methanol 200 g, and polybromodiphenyl ether (known as an addition-type brominated flame retardant) 1
30 g and 150 g of triphenyl phosphate were added to make a varnish.

The varnish obtained as described above was adjusted to a resin content of 48%. A kraft paper impregnated and dried with a water-soluble phenol resin was prepared, impregnated with the varnish described above, and dried to obtain a prepreg. A predetermined number of the prepregs are stacked, and a copper foil with an adhesive is stacked on one side, and 10MP
a, Heating and pressing at 160 ° C. for 1 hour to produce a copper-clad laminate. The characteristics of the obtained copper-clad laminate were measured in accordance with JIS-6481.
It measured according to. The results are shown in Tables 1 to 5.

[0033]

[Table 1] ─────────────────────────────────── Insulation resistance (unit: Ω); Upper: receiving state, lower: D-2 / 100 ─────────────────────────────────── Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 2.7 × 10 ¹² 1.4 × 10 ¹² 0.9 × 10 ¹² 6.7 × 10 ¹² 1.8 × 10 ¹² 1.1 × 10 ¹² 2.8 × 10 ⁸ 1.6 × 10 ⁸ 2.3 × 10 ⁸ 4.3 × 10 ⁸ 1.6 × 10 ⁶ 1.9 × 10 ⁸ ───────────────────────────────────

[0034]

[Table 2] 耐熱 Solder heat resistance (unit: seconds) ─── ──────────────────────────────── Example 1 Example 2 Example 3 Example 4 Example 4 Comparative Example 1 Comparative Example 2 33 31 28 39 65 ───────────────────────────────────

[0035]

[Table 3] ト リ Trichlorethylene resistance (to boiling trichlorethylene) (Immersion) ─────────────────────────────────── Example 1 Example 2 Example 3 Example 4 Comparison Example 1 Comparative Example 2 30 minutes 30 minutes 30 minutes 30 minutes 1 minute 1 minute No abnormality No abnormality No abnormality No abnormality No surface whitening Surface whitening ─────────────────── ────────────────

[0036]

[Table 4] 性 Punching workability ──────── ─────────────────────────── Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 40 to 100 ° C. 40 ~ 110 ℃ 40 ~ 90 ℃ 40 ~ 110 ℃ Bulge occurrence Bulge occurrence Good Good Good Good ─────────────────────────────── ────

[0037]

[Table 5] 燃 Flame retardant (UL-94); Processing conditions , Upper: receiving state, lower: E-3 / 130 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V −0 ───────────────────────────────────

[0038]

According to the present invention, dry oil or semi-dry oil which is inexpensive and has a stable supply, such as linseed oil, is used as a modifier for phenolic resins for flame-retardant laminates, and furthermore, tung oil is used as a modifier. A flame-retardant phenol resin laminate equivalent to the flame-retardant phenol resin laminate can be obtained.

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Takeshi Horiuchi 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Industry Co., Ltd.Shimodate Research Laboratory (72) Inventor Kenichi Ikeda 1500 Oji Ogawa Shimodate City, Ibaraki Prefecture Hitachi Chemical Inside Shimodate Plant Co., Ltd. (72) Inventor Yoshiyuki Narabe 1500, Oji Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Shitadate Plant Co., Ltd. (72) Yoshihiro Nakamura 1500 Ogawa Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical (56) References JP-A-63-83141 (JP, A) JP-A-63-83140 (JP, A) JP-A-54-129087 (JP, A) JP-A-5-5022 ( JP, A) JP-A-4-168122 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B29B 11/16 B29B 15/08-15 / 14 C08J 5/04-5/10 C08J 5/24 H05K 1/03

Claims (3)

(57) [Claims] 1. A phenol compound is added to a drying oil or a semi-dry oil containing linoleic acid and / or linolenic acid as a main component, using perfluoroalkanesulfonic acid as a catalyst, and resolving the phenol. A prepreg obtained by impregnating and drying a fibrous base material with a resin varnish containing a vegetable oil-modified phenolic resin and an epoxy resin-based reactive flame retardant as essential components is stacked and heated and pressurized. Of manufacturing a functional laminate. 2. The method for producing a flame-retardant laminate according to claim 1, wherein a phenol is added to the drying oil or the semi-drying oil in the presence of an aromatic hydrocarbon formaldehyde resin. 3. The drying oil or the semi-drying oil containing a conjugated double bond in the molecule is reacted with the drying oil or the semi-drying oil to which phenols are added. Or the method for producing a flame-retardant laminate according to 2.