JPH0579092B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a phenolic resin modified with Oiticica oil, which is used when producing a phenolic resin laminate used in electronic equipment. Prior Art Conventionally, phenolic resin modified with tung oil has been widely used for phenolic resin laminates or copper-clad laminates. Tung oil has a conjugated double bond and has excellent reactivity with phenols, so by using the modified phenolic resin, a laminate with excellent electrical performance and punching workability was obtained. The above-mentioned tung oil has a problem in that the price fluctuates significantly and it is difficult to secure a stable raw material. Therefore, Oiticica oil, which is used as a substitute for tung oil, is a raw material that is more stable in price than tung oil, and its main component is α-lycanic acid, which has a conjugated triene structure similar to α-eleostearic acid, the main component of tung oil. Therefore, it exhibits reactivity very similar to tung oil. However, α-lycanic acid differs from α-eleostearic acid in that it has a keto group in its molecular chain, which makes it different in its reactivity with phenols. In addition, Oiticica oil is
It has a higher content of saturated aliphatics than tung oil. Furthermore, there are differences such as higher viscosity, and compatibility with phenolic resins is also different. Problems to be Solved by the Invention For example, when an oiticica oil-phenol adduct is reacted with formaldehyde under a basic catalyst to form a resol, the compatibility of the resin composition is poor and a transparent and uniform cured product cannot be obtained. hard. Further, when the basic catalyst is a tertiary amine catalyst, the reactivity is extremely poor, and when an ammonia catalyst or the like is used, there is a drawback that the impregnating property into the base material for the laminate is poor. The object of the present invention is to obtain an Oiticica oil-modified phenolic resin that is suitable for manufacturing laminates and can provide laminates with good properties. Means for Solving the Problems The present invention involves first reacting phenols and Oiticica oil in the presence of an acidic catalyst to produce an Oiticica oil-phenol adduct, and then using a lower aliphatic alcohol solvent in the presence of a tertiary amine catalyst. This is a method for producing Oiticica oil-modified phenol resin, which is characterized by reacting it with formaldehyde in the reactor and further adding a secondary amine catalyst to form a resol. Effects In the present invention, in the resolization reaction, the lower aliphatic alcohol solvent homogenizes the system and suppresses rapid polymer production. Then, by first reacting in the presence of a tertiary amine as a basic catalyst, a reaction system with less polymer formation and many methylol groups is generated, and then by reacting in the presence of a secondary amine catalyst, curing is performed. A resin varnish with high crosslinking density can be obtained at a high speed. Examples Phenols used in the present invention include carbolic acid, cresol, xylenol, butylphenol, octylphenol, nonylphenol, oak nut oil, urushiol, resorcinol, naphthol, and novolak bisphenol A of the above phenols. . Further, the acidic catalyst used in the present invention includes inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as toluenesulfonic acid and xylenesulfonic acid, and Lewis acids. The Oiticica oil-phenol adduct obtained in the presence of an acidic catalyst is then reacted with formaldehyde in a lower aliphatic alcohol solvent in the presence of a tertiary amine catalyst, and the reaction further proceeds under a secondary amine catalyst to form a resol. become Examples of the tertiary amine used in the present invention include trimethylamine, triethylamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-methylimidazole,
2-phenylimidazole, 2-ethyl 4-methylimidazole, etc. are suitable. Further, as the secondary amine used in the present invention, dimethylamine, dipropylamine, diethylamine, diisobutylamine, etc. are suitable. For formaldehyde, high concentration 80
Preferably, ~90% paraformaldehyde is used. The appropriate molar ratio of formaldehyde to phenols is 1.1 to 1.3 moles. Incidentally, during the resolization reaction in a lower aliphatic alcohol solvent under a tertiary amine catalyst, the above-mentioned phenols may be added as necessary. Further, the lower aliphatic alcohol used in the present invention preferably has 3 or less carbon atoms, such as methanol, ethanol, and propyl alcohol. The Oiticica oil-modified phenolic resin according to the present invention is obtained by impregnating a base material such as cotton linter paper or kraft paper, then stacking the required number of sheets, and if necessary, further layering copper foil on one or both sides and heating and pressing. Obtain a laminate or copper-clad laminate. Furthermore, when impregnating a substrate with the Oiticica oil-modified phenolic resin according to the present invention, it is also possible to mix a water-soluble phenolic resin initial condensate or to use a substrate pre-impregnated with the aforementioned initial condensate. Example 1 Add 500 g of phenol, 500 g of oiticica oil, and 0.5 g of paratoluenesulfonic acid, and heat at 95 to 100°C.
The reaction was carried out for 120 minutes to obtain an oiticica oil-phenol adduct. Subsequently, 68 g of methanol, 27 g of triethylamine, and 220 g of 85% paraformaldehyde were added and reacted for 3 hours at 95 to 100°C, then 7 g of diethylamine was added and reacted for another 4 hours at 95 to 100°C, resulting in a resol varnish with a gel time (160°C) of 3 minutes. Obtained. This varnish was diluted with methanol to obtain a 50% concentration oiticica oil modified phenolic resin varnish. Kraft paper was impregnated with the Oiticica oil-modified phenolic resin varnish and dried to obtain coated paper with a resin adhesion content of 48% by weight. Eight plies of the coated paper and a 35μ thick copper foil coated with adhesive were layered on one side of the coated paper, and heated and pressed at 160° C. and 100 kgf/cm ³ for 60 minutes to obtain a 1.6 mm thick copper clad laminate. Its performance is shown in Table 1. Comparative Example 1 Add 500 g of phenol, 500 g of oiticica oil, and 0.5 g of paratoluenesulfonic acid, and heat at 95 to 100℃.
The reaction was carried out for 120 minutes to obtain an oiticica oil-phenol adduct. Subsequently, 68 g of methanol, 27 g of triethylamine, and 220 g of 85% paraformaldehyde were added and reacted at 95 to 100°C for 8 hours to give a gel time of 3 minutes 40
A second resol varnish was obtained (gelation did not proceed after 6 hours and the viscosity in the system increased, making it impossible to continue the reaction for more than 8 hours). Using the above varnish, the thickness was determined in the same manner as in Example 1.
A 1.6 mm copper clad laminate was obtained. Its performance is shown in Table 1.

【table】

[Table] Effects of the Invention The Oiticica oil-modified phenolic resin according to the present invention is converted into a resol using a tertiary amine catalyst to obtain a varnish with a large number of methylol groups in the system, and then converted into a polymer using a secondary amine catalyst. The resulting varnish has improved impregnating properties with respect to the base material, and a cured product with high crosslinking density can be obtained, resulting in a laminate with excellent electrical properties, water resistance, and good interlayer adhesion during punching. can be obtained. In addition, as shown in Table 1, since the varnish volatilization rate is low, it has excellent productivity such as material yield, and has extremely great industrial value.

Claims (1)

[Claims] 1. After reacting phenols and oiticica oil in the presence of an acidic catalyst, in the presence of a tertiary amine catalyst,
A method for producing an oil-modified phenolic resin, which comprises reacting with formaldehyde in a lower aliphatic alcohol solvent and further reacting under a secondary amine catalyst.