JPH0548251B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a resin composition for a laminate having excellent processability and electrical properties. [Technical background of the invention and its problems] In recent years, with the remarkable development of the electronics industry, the conditions for using printed wiring boards have become harsher, and the characteristics required of the boards are becoming increasingly strict. In particular, with the trend toward chipping, automatic insertion, and high-density patterning of components, there is an increasing need for laminates with superior electrical properties, physical properties, and workability. Conventionally, phenolic resin laminates have used some phenolic resins modified with melamine to improve their arc resistance and tracking resistance, but melamine modification has improved moisture resistance, low-temperature punching properties, and dimensional stability. However, there was a problem that the quality and other characteristics were slightly decreased. [Object of the Invention] The present invention was made to solve these difficulties, and provides a resin composition for laminates that has improved moisture resistance, low-temperature punching properties, and dimensional stability of a melamine-modified phenolic resin. The purpose is to [Summary of the Invention] That is, the resin composition of the present invention is characterized by comprising the following components. (a) A composition comprising a xylene resin or mesitylene resin, a phenol or a methylolated melamine, and an acidic catalyst, (b) formaldehyde, and (c) a basic catalyst. As the xylene resin used in the present invention, one having an oxygen content of 9 to 14% and an average molecular weight of 300 to 600 is suitable, such as Nicanol H manufactured by Mitsubishi Gas Chemical Company. Further, as the mesitylene resin, one having an oxygen content of 10 to 14% and an average molecular weight of 300 to 550 is suitable. The phenols used in the present invention include phenols, alkylphenols such as cresol and xylenol, arylphenols such as phenylphenol and cumylphenol, halogenated phenols, and polyhydric phenols such as bisphenol A. In addition, it is also possible to use a product obtained by reacting these with a drying oil such as tung oil. Melamines used in the present invention include guanamines such as formguanamine, acetoguanamine, and benzoguanamine in addition to melamine. Examples of the methylolated melamines used in the present invention include methylolated products of the above-mentioned melamines. Acidic catalysts used in the present invention include organic sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid, organic sulfonic acid salts such as toluenesulfonic acid chloride, and metal chlorides such as tin chloride and zinc chloride. Contains inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, and organic acids such as formic acid and oxalic acid. The basic catalysts used in the present invention include ammonia, amines such as hexamethylenetetramine, triethanolamine, monomethylamine, and ethylenediamine, and alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide. Examples include hydroxides of metals and alkaline earth metals, and inorganic salts such as sodium carbonate. Formaldehyde used in the present invention includes:
Examples include formalin solution or paraformaldehyde. In the present invention, first, an acidic catalyst is added to a xylene resin or a mesitylene resin, a phenol, and optionally a methylolated melamine, and the mixture is reacted under strong acidity at a temperature of 80 to 150°C for 0.5 to 3 hours. A basic catalyst is added to the obtained reaction product to neutralize it, and in the pH range of 5 to 9, it is mixed with formaldehyde and optionally melamine at 80 to 150°C.
React for a period of time to form a resol. Next, the reaction solution is dehydrated under reduced pressure to obtain the resin composition for a laminate of the present invention. In the present invention, a flame-retardant resin composition for laminates can be obtained by adding a general-purpose flame retardant to this resin composition for laminates. The thus obtained resin composition for laminates is dissolved and diluted in an organic solvent, impregnated into a paper base material such as kraft paper, and after laminating a plurality of sheets, the resin composition is heated and press-molded to achieve the desired purpose. A laminate is obtained. [Examples of the invention] Next, examples of the invention will be described. Example Nicanol H75 in a four-necked flask with a condenser
g, phenol 100g, tung oil 100g, Nicaresin S
-260 (manufactured by Nippon Carbide Kogyo Co., Ltd., trade name of methylolated melamine) 100g and para-toluenesulfonic acid 0.27g were reacted at 100℃ for 1 hour, then 240g of 37% formalin was added and the pH was adjusted to 7 with monomethylamine. The mixture was reacted at 100°C for 2 hours. After the reaction, dehydrate under reduced pressure and toluene:methanol=
Diluted with 1:1 solution, resin solids content 55%, viscosity 3.5
A varnish with poise (25°C) and gelling time of 2 minutes (150°C) was prepared. Comparative example 1 Phenol 129 in a four-necked flask with a condenser
g, tung oil 100g, para-toluenesulfonic acid 0.27g
and react in the same manner as in the example,
A varnish with a resin solid content of 55%, a viscosity of 2.0 poise (25°C), and a gelation time of 3 minutes (150°C) was prepared. Comparative Example 2 YDB-400 and YDB-400 were added to the resin composition obtained in Comparative Example 1.
A varnish with a gelation time of 2 minutes and 30 seconds (150°C) was prepared by mixing CDP to have a bromination rate of 10% and a phosphorylation rate of 1%. Comparative example 3 Phenol 200 in a four-necked flask with a condenser
g, 100 g of tung oil, and 0.3 g of para-toluenesulfonic acid sulfonic acid were charged and reacted at 100°C for 1 hour, then 260 g of 37% formalin was added, the pH was adjusted to 6 with monomethylamine, and the reaction was allowed to proceed at 100°C for 2 hours.
After the reaction, it was dehydrated under reduced pressure, and toluene:methanol=1:
A varnish with a resin solid content of 55%, a viscosity of 1.5 poise (at 25°C), and a gelation time of 3 minutes and 10 seconds (at 150°C) was prepared by diluting with 1 solution. The resin compositions obtained in the above Examples and Comparative Examples
Impregnated and coated on 10 mil kraft paper, resin impregnation amount 50
Processed paper with a resin flow of 8% by weight was obtained. Layer 8 sheets of processed paper and 1 sheet of copper foil with adhesive,
Molding was carried out for 75 minutes at 170° C. and 100 kg/cm ² to obtain a copper-clad laminate with a thickness of 1.6 mm. The test results regarding the properties of the obtained copper-clad laminate are shown in the table.

[Table] [Effects of the Invention] As is clear from the above explanation, the laminate using the resin composition for laminates of the present invention has improved moisture resistance, low-temperature punchability, and dimensional stability, and has excellent electrical properties. ing.

Claims (1)

[Scope of Claims] 1. A resin composition for a laminate, characterized by comprising the following components: (a) A composition comprising a xylene resin or mesitylene resin, a phenol or a methylolated melamine, and an acidic catalyst, (b) formaldehyde, and (c) a basic catalyst.