JPH0952927A - Production of phenol resin modified with diene polymer added with phenol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin giving a copper-clad laminated sheet excellent in flexibility and punching quality by carrying out the addition reaction of a phenol to a diene polymer in the presence of a superstrong acid and then allowing the addition product to react with formaldehyde in the presence of a basic catalyst. SOLUTION: This resin is produced by the addition of phenol (e.g. phenol, resorcin, etc.) to a diene polymer (polyisoprene, polybutadiene or polychloroprene are preferred) in the presence of a superstrong acid (such as pentafluoroethane sulfonic acid) preferable at 80-150 deg.C under reflux and then the reaction product is allowed to react with formaldehyde to perform resole formation preferably at 60-90 deg.C in a solvent. Preferably, a 50-1000 pts. of phenol is added per 100wt. pts. of the diene polymer in the presence of 0.05-0.2 pts. of a superstrong acid. The molar ratio of formaldehyde to phenol is preferably set at 1.2-1.6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol-added diene polymer modified phenol resin suitable for a method for producing a copper clad laminate excellent in punching workability.

[0002]

2. Description of the Related Art A paper-phenol laminated plate is punched or punched by a die to form an outer shape. In recent years, in order to reduce the dimensional change of printed wiring boards, there is a tendency to punch at room temperature without heating the punching process. Therefore, a flexible phenol resin has been used in order to improve the punching process of the laminated plate. As a method for making the phenolic resin flexible, phosphoric acid esters containing eleostearic acid as a main component and rich in reactivity, such as tung oil and triphenyl phosphate, are commonly used.

However, since tung oil is a natural product, price fluctuations are severe due to natural disasters such as abnormal weather, floods, earthquakes, and human factors, and it is often difficult to obtain it. Further, the flexibility due to the phosphoric acid ester has a problem in solvent resistance and electric characteristics of the laminated plate, and it is difficult to realize the low temperature punching workability only with the phosphoric acid ester. Therefore, it has been proposed to use a petroleum long-chain compound such as liquid polybutadiene, which is stable in price, as a flexibility improving agent for laminated sheets (Japanese Patent Laid-Open No. 50-15864).
5 and JP-A-55-108447).

[0004]

However, unlike tung oil, these long-chain diene compounds do not have a conjugated triene structure. Therefore, the reaction with phenols is difficult with general organic acids such as p-toluenesulfonic acid,
It was difficult to obtain a resin having good compatibility with the phenol resin.

The present invention has been made in view of the above situation, and is excellent in compatibility, flexibility and punching by using a diene polymer which is an extremely stable raw material in terms of price or supply amount. An object is to provide a phenol-added diene-based polymer-modified phenol resin suitable for a phenol resin laminate having excellent properties.

[0006]

[Means for Solving the Problems] The present invention comprises adding a phenol to a diene polymer in the presence of a super strong acid,
Then, the formaldehyde is reacted in the presence of a basic catalyst.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The diene-based polymers and the phenols are mixed in an amount of 50 to 1,000 parts of the phenols with respect to 100 parts of the diene-based polymers (the same applies hereafter by weight) in the presence of a super strong acid. Allow the addition reaction. As the super strong acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, trifluoromethanesulfonic acid, etc. are used. For 100 parts by weight of diene polymer,
The superacid is used in a proportion of 0.01 to 1 part, preferably 0.05 to 0.2 part.

The diene polymer is not particularly limited, and any diene polymer can be used. A diene polymer selected from polyisoprene, polybutadiene or polychloroprene is preferred.

As the phenols, phenol, resorcin, catechol, m-cresol, o-cresol, octylphenol, nonylphenol, tert-butylphenol, xylenol, etc. which are used in ordinary phenol resin synthesis can be used.

The reaction between the diene polymer and the phenol is generally preferably carried out under reflux at a temperature of 80 to 150 ° C.

After reacting the diene polymer with the phenols, a basic catalyst and formaldehyde are added,
The reaction is carried out at 0 to 90 ° C. to form a resole. This reaction is
It is preferably carried out in a solvent. By this reaction, phenol of the phenol-added diene polymer is condensed with formaldehyde to form a resol resin to which the diene polymer is added. The resol resin thus obtained is molded into a laminate according to a conventional method. When there are phenols remaining after the reaction between the diene polymer and the phenols, the phenols are also condensed. From the viewpoint of punching workability after forming into a laminate, if necessary, phenols are added at the time of resolization.

As the formaldehyde source, formalin, paraformaldehyde, trioxane and the like are used. The amount of formaldehyde to be added is such that when the number of moles of phenols present in the reaction system is P and the number of moles of formaldehyde to be added is F, (F / P) is greater than 1.0, preferably (F / P). / P) is 1.2 to 1.6. If the reaction molar ratio is less than 1.0, resol cannot be obtained.

As the basic catalyst, sodium hydroxide,
Any alkaline substance such as potassium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, etc., which is used in ordinary resol synthesis, can be used. The amount of the basic catalyst is an amount that can make the reaction system alkaline after addition.

According to the production method of the present invention, since phenols are added to the diene polymers, the diene polymers are treated with a flexing agent for the phenol resin in the same manner as the phenol resin modified with tung oil. Can be Therefore, it is possible to obtain a laminated plate having the same solder heat resistance and punching workability as that of the laminated plate using tung oil as a flexibilizing agent, without using tung oil.

[0015]

【Example】

Example 1 450 g of phenol, 45 g of polyisoprene, and 92 μl of trifluoromethanesulfonic acid were added to a 1-liter flask equipped with a stirrer, a condenser, and a thermometer, and the mixture was mixed at 100 ° C. for 3 days.
After reacting for a time, 189 g of toluene, 189 g of 92% paraform and 33 g of 25% ammonia water were added, and the mixture was refluxed at 80 ° C. The gelling time was measured on a 160 ° C. heating plate, and the reaction was terminated when the gelling time reached 4 minutes.

Example 2 Phenol (450 g), polyisoprene (45 g) and trifluoromethanesulfonic acid (92 μl) were added to a 1 liter flask equipped with a stirrer, a condenser and a thermometer, and the mixture was stirred at 100 ° C. for 3 days.
After reacting for a time, 189 g of toluene, 189 g of 92% paraform and 15 g of triethylamine were added, and the mixture was refluxed at 80 ° C. The gelation time was measured in the same manner as in Example 1, and the reaction was terminated when the gelation time reached 4 minutes.

Comparative Example 1 450 g of phenol, 45 g of polyisoprene and 0.9 g of p-toluenesulfonic acid were added to a 1 liter flask equipped with a stirrer, a cooler and a thermometer, and after reacting at 100 ° C. for 3 hours, Toluene 189g, 92% paraform 18
9 g and triethylamine 15 g were added and the mixture was refluxed.
The gelling time was measured in the same manner as in Example 1, and the gelling time was 4
The reaction was terminated when the time reached. The resin cured product became cloudy and became opaque when formed into a laminated plate, which was not suitable as a resin for laminated plates.

Comparative Example 2 In a 1 liter flask equipped with a stirrer, a condenser and a thermometer, 100 g of phenol, 25 g of xylene resin (trade name: Nikanol-H, manufactured by Mitsubishi Gas Chemical Co., Inc.), and 0.5 g of p-toluenesulfonic acid were added. It was charged and reacted at 100 ° C. for 1 hour.
Then, 100 g of tung oil was added and reacted at the same temperature for 5 hours. 90 g of phenol and paraform 1 after the reaction
28 g, 40 g of methanol, and 38 g of aqueous ammonia were added to carry out a resolization reaction at 80 ° C. The reaction was terminated when the gelation time at 160 ° C. reached 6 minutes.
Next, 100 g of toluene and 100 g of methanol were added to form a varnish.

The varnish obtained above (excluding Comparative Example 1)
A prepreg was prepared by impregnating a kraft paper impregnated with a water-soluble phenol resin to a resin content of 48% and impregnating it with water, followed by drying. Eight sheets of this prepreg were stacked, a copper foil with an adhesive was stacked on one side, and heated and pressed at a temperature of 160 ° C. and a pressure of 10 MPa for 1 hour to manufacture a copper-clad laminate.

The copper-clad laminate thus obtained was immersed in water in a receiving state and at 100 ° C. for 2 hours (D-2 /
After 100), the insulation resistance, solder heat resistance and punching workability at 40 ° C. were examined. The test method is JIS-C648.
Compliant with 1. Table 1 shows the results. In Table 1,
Insulation resistance 1 is the insulation resistance in the receiving state, insulation resistance 2 is (D-
The insulation resistance is 2/100).

[0021]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Item Example 1 Example 2 Comparative example 2 ─ ────────────────────────────────── Insulation resistance 1 (Ω) 1.9 × 10 ¹³ 1.3 × 10 ¹³ 5.9 × 10 ¹² Insulation resistance 2 (Ω) 2.7 × 10 ⁸ 2.8 × 10 ⁸ 5.7 × 10 ⁸ Soldering heat resistance (s) 43 38 45 Good punching workability Good Good Good ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0022]

EFFECT OF THE INVENTION Since phenols are added to the diene polymers in the presence of a super strong acid and then formaldehyde is reacted in the presence of a basic catalyst, the diene polymers are chemically bonded to the phenols. are doing. Therefore, the laminated board using the resin obtained by resolizing this as a matrix has the same solder heat resistance and punching workability as those of the tung oil-modified phenol resin. According to the invention,
Different from natural products such as tung oil, it has become possible to use diene polymers that are stable in supply as phenol resin modifiers.

Claims (3)

[Claims] 1. A phenol-added diene-based polymer-modified phenol resin, which is characterized in that a phenol is added to a diene-based polymer in the presence of a super strong acid, and then formaldehyde is reacted in the presence of a basic catalyst. Production method. 2. The diene polymer is polyisoprene,
The method for producing a phenol-added diene polymer-modified phenol resin according to claim 1, which is a diene polymer selected from polybutadiene or polychloroprene. 3. The phenol-added diene polymer according to claim 1 or 2, wherein the super strong acid is a super strong acid selected from pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid and trifluoromethanesulfonic acid. A method for producing a modified phenolic resin.