JPS6021697B2 - Method for manufacturing flame-retardant phenolic resin laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a flame-retardant phenolic resin laminate, and its purpose is to achieve flame retardancy while maintaining electrical insulation resistance, impact resistance, and punching workability. It's about improving.

Conventionally, phosphoric acid esters and halogen compounds were added to phenolic resins in order to improve their flame retardancy, which was a drawback of phenolic resins, but the addition of phosphoric acid esters and halogen compounds greatly increased the permeability into the base material for laminates, etc. It also has the disadvantage of lowering the crosslinking density of phenolic resin, so when phenolic resin laminates are used, although flame retardance is improved, electrical insulation resistance, impact resistance, punching workability, etc. The reality is that the decline in the economy cannot be stopped.

The present inventors have conducted extensive research to improve the above-mentioned drawbacks, and as a result, have arrived at the present invention.

That is, P-isoprobenylphenol or P-isoprobenylphenol oligomer alone or a mixture thereof is reacted with an aldehyde, and then reacted with monochloridate phosphate, and then the phenol and the aldehyde are reacted. A flame-retardant ferresin obtained by adding and reacting with B} is impregnated into the base material for the laminate, dried to obtain a resin-impregnated base material, and a predetermined number of sheets are laminated. This is a method for producing a flame-retardant phenolic resin laminate, characterized in that copper foil is stacked on at least one side, or the copper foil is integrated by heating and pressurizing without stacking. In the present invention, first, preferably 0.7 to 2 moles of an aldehyde such as formalin or paraformaldehyde is added to 1 mole of P-isoprobenylphenol or P-isoprobenylphenol oligomer alone or a mixture thereof. Then, the mixture is reacted at reflux temperature for 30 to 190 minutes under an alkaline catalyst such as sodium hydroxide, aqueous ammonia, or an amine, or an acidic soot such as hydrochloric acid or cyanoic acid.

Next used P-isoprobenylphenol or P-
General formula (R: alkyl group of C, ~C, 2, X: Br, CL, e: 1-3, m: 1-3
, e0m≦3) For example, diphenyl phosphate monochloridate, dicresyl phosphate monochloridate, dipropylphenyl phosphate monochloridate, dinonylphenyl phosphate monochloridate, di(monobromphenyl) phosphate monochloridate , di(tribromocrezyl)
Phosphoric acid monochloridate, di(dichlorophenyl) phosphoric acid monochloridate, general formula (R: C2 to C,2 alkyl group, X: day, Br, CL, m: 1 to
Compounds represented by 2), such as diethyl phosphate monochloridate, dipropyl phosphate monochloridate, dioctyl phosphate monochloridate, di(dic).

Preferably 1 mol of monochloridate phosphates, such as monochloridate di(promoethyl)monochloridate, monochloridate di(dichloropropyl)monochloridate, monochloridate di(bromoethyl)phosphate, or a mixture thereof. Add and react. Sodium hydroxide, potassium hydroxide,
1 to 1.1 mol of a dehydrohalogenating agent such as a tertiary amine is added and reacted.

Also, by-product salts are removed by washing with water. The reaction products obtained next include phenols such as phenol, cresol, xylene, xylenol, P-isoprobenylphenol, and P-isoprobenylphenol oligomer, and aldehydes such as formalin and paraformaldehyde {B)
is added so that the phosphorus content is preferably 0.8 to 3% by weight (hereinafter referred to as %) based on the solid content of the flame-retardant phenol resin finally obtained, and aldehyde [B} is added to 1 mol of phenol. Preferably, 1.2 to 2 mol is added to the amine, calcium hydroxide, magnesium hydroxide, etc.
After adjusting H to 8-10 and reacting at reflux temperature for 30-360 minutes, a flame-retardant phenolic resin is obtained. The phosphorus content of flame-retardant phenolic resin is 0 relative to the solid content of phenolic resin.
．． When it is less than 8%, there is no effect on flame retardancy and punching workability when it is made into a laminate, and when it exceeds 3%, the bending strength and punching workability tend to decrease when it is made into a laminate. .

Next, the flame-retardant phenolic resin is diluted with a diluent such as methyl alcohol, made into a solution, and impregnated into a base material for a laminate such as kraft paper, linter paper, cotton cloth, synthetic fiber cloth, or synthetic fiber nonwoven fabric.

The resin solid content contained in the resin soaked base material is preferably 20 to 70%.

A predetermined number of dried resin-impregnated substrates are layered, heated and pressurized to obtain a flame-retardant phenolic resin laminate.

If copper foil is layered on one or both of the upper and lower outer surfaces of the laminated horizontal fat-impregnated base material and heated and pressed, a copper-clad laminate is obtained.

The flame-retardant phenolic resin laminate obtained according to the method of the present invention exhibits excellent properties such as insulation resistance, bending strength, flame retardance, and punching workability.

Example 1 P-isoprobenylphenol oligomer (dimer) 1
34 (0.5 mol), 50% formalin 369 (0.
6 mol), triethylamine was added overnight and the mixture was heated to 60 mol at reflux temperature.
After reacting for 1 minute, sodium hydroxide was added for 40 hours, dicresyl phosphate monochloridate was added for 299 hours (1.0 female mol).
was added and reacted at 40 to 50 degrees C for 60 minutes to obtain a reaction product.

Next, this reaction product is 100% of phenol and 110% of phenol (1
．． 17 moles), 50% formalin (1.75 moles) was added, 3 cc of triethylamine was added, the reaction was carried out for 10 minutes at reflux temperature, and the phosphorus content was diluted with 150 moles of ethyl alcohol. A flame retardant phenolic resin with a content of 2.85% was obtained.

The above flame-retardant phenolic resin is impregnated with the 0.1-thickness kraft paper so that the resin content is 53%, dried to obtain resin-impregnated paper, and a laminate of 8 sheets of this resin-impregnated paper is made. Sandwiched between mold metal plates, molding pressure 120k9/ground, 150q
Laminate molding was carried out for 60 minutes at a temperature of 1.0 m to obtain a flame-retardant phenolic resin laminate having a thickness of 1.6 mm. Example 2 Reaction product obtained in the same manner as in Example 1: 100% cresol 200% (1.85 mol), 37% formalin 21%
After adding 0.0 mol (2.59 mol), 15 cc of 25% ammonia water was added and reacted for 180 minutes at reflux temperature, and then diluted with 250 ml of dichloroethyl alcohol to obtain a solution with a phosphorus content of 2% based on the resin solid content. Obtain a flammable phenolic resin, then Example 1
A flame-retardant phenolic resin laminate was obtained in the same manner as above.

Example 3P-isoprobenylphenol oligomer (
dimer) 134 (0.5 mol), 37% formalin 3
Add 1 night of oxalic acid (0.6 mol) and boil at reflux temperature to 120
After reacting for minutes, sodium hydroxide was added for 44 min, then di(
Dichloropropyl) phosphate monochloridate 3 paper. 5th evening (
1 mol) was added and reacted at 40 to 50 oo for 60 minutes to obtain a reaction product.

Next, this reaction product is 100% of phenol, 240% of phenol (2
．． 55 mol), 245 mol (4.08 mol) of 50% formalin was added, 4 cc of diethylamine was added, the reaction was carried out at reflux temperature for 80 minutes, and then diluted with 280 mol of alcohol to reduce the phosphorus content to the resin solid content. A 2% flame retardant phenol resin was obtained, and then treated in the same manner as in Example 1 to obtain a flame retardant phenol resin laminate.

Example 4 To the reaction product 50 obtained in the same manner as in Example 3, 270 mol of cresol (2.5 mol) and 30 ml of 37% formalin (375 mol) were added, then 5 cc of triethylamine and 1 cc of diethylamine were added, and the mixture was heated to reflux temperature. So 12
After reacting for 0 minutes, it was diluted with 250 ml of alcohol to obtain a flame-retardant phenol resin with a phenol content of 1.0% based on the resin solid content, and then treated in the same manner as in Example 1 to make it flame-retardant. A phenolic resin laminate was obtained.

Comparative Example 1 A common phenolic resin varnish for laminates was treated in the same manner as in Example 1 to obtain a phenolic resin laminate.

Comparative Example 2 Tung oil-modified phenolic resin varnish for laminates was prepared by adding 5 parts of tetrabromobisphenol AI and 3 parts of antimony trioxide to obtain a flame-retardant phenol resin, and then treated in the same manner as in Example 1 to obtain a flame-retardant phenol resin. A resin laminate was obtained.

Comparative Example 3 Same reactant as Example 1: 100% cresol 65% 50%
Add 47% formalin and then 25% ammonia water 5%
After adding cc and reacting for 8 powders at reflux temperature, diluted with 150 ml of chloroalcohol until the phosphorus content was 4% based on the resin solid content.
．． A flame-retardant phenol resin of No. 1 was obtained, and then treated in the same manner as in Example 1 to obtain a flame-retardant phenol resin laminate.

Table 1 shows the test results of the above phenolic resin laminate.

However, the insulation resistance and bending strength after treatment are JIS C 648.
Flame retardancy was measured according to UL Standard Sub94. Table 1 As is clear from Table 1, the flame-retardant phenolic resin laminate using the flame-retardant phenol resin obtained according to the present invention has excellent insulation resistance, bending strength, flame retardancy, punching workability, and falling ball impact. It has excellent performance in terms of properties, etc.

Claims (1)

[Claims] 1 P-isopropenylphenol or P-isopropenylphenol oligomer alone or a mixture thereof is reacted with an aldehyde (A), and then reacted with phosphoric acid monochloridate, and further reacted with a phenol. A flame-retardant phenolic resin obtained by adding and reacting aldehydes (B) and a flame-retardant phenolic resin is impregnated into a base material for a laminate, dried to obtain a resin-impregnated base material, and a predetermined number of sheets are laminated. A method for producing a flame-retardant phenolic resin laminate, which comprises stacking copper foil on at least one side, or heating and pressurizing the copper foil without stacking it to integrate it. 2. The flame retardant according to claim 1, wherein the amount of aldehyde (A) is 0.7 to 2 moles per mole of P-isopropenylphenol or P-isopropenylphenol oligomer. A method for producing a phenolic resin laminate. 3. The problem according to claim 1 or 2, wherein the amount of phosphoric acid monochloridate is 1 mole per hydroxyl group of P-isopropenylphenol or P-isopropenylphenol oligomer. A method for producing a flammable phenolic resin laminate. 4. The flame-retardant phenol according to claim 1, 2 or 3, wherein the amount of the aldehyde (B) is 1.2 to 2 mol per 1 mol of the phenol. Method for manufacturing resin laminates. 5. Claims 1, 2, 3, or 4, characterized in that the phosphorus content of the flame-retardant phenolic resin is 0.8 to 3% by weight based on the solid content of the phenolic resin. A method for producing a flame-retardant phenolic resin laminate as described in 2.