JPH0717766B2 - Laminated board manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a drying oil-modified phenolic resole resin laminate having good punchability.

(Prior Art) A phenolic resole resin is used for a laminated board used for a printed wiring board.

Resole resins are usually phenols and formaldehyde reacted under a base catalyst and lack flexibility as they are, so they are modified with a drying oil or the like.

Phenols for producing a dry oil-modified phenolic resole resin include phenol, metacresol, paracresol, orthocresol, paraisopropylphenol, paratertiarybutylphenol, oligomers of paraisopropenylphenol, nonylphenol,
Bisphenol A or the like is used.

As the drying oil, tung oil, dehydrated castor oil, or sardine oil and the like are used.

Recently, as printed wiring boards used in electronic devices have become higher in density, automatic component mounting technology has also become more precise and stricter dimensional accuracy is required. To meet this requirement, low temperature punching has been performed. ing.

In order to improve punching workability, a resin has been conventionally modified with a plasticizer. There are two ways to modify the resin with a plasticizer, one is with an external plasticizer,
The other is due to the internal plasticizer.

Phosphates, polyethers, etc. are used as the external plasticizer, and higher fatty acid esters, polybutadiene, etc. are used as the internal plasticizer.

(Problems to be Solved by the Invention) However, when a large amount of the external plasticizer is used, the punching processability and the solvent resistance are significantly reduced due to the decrease in the resin crosslink density. In addition, when a large amount of higher fatty acid esters and polybutadienes are used, the whitening (bulge) around the punching hole during the punching process remarkably occurs, and the compatibility with the phenol resin decreases significantly, resulting in a uniform impregnation. No varnish can be obtained and the molded laminate becomes opaque, resulting in large variations in quality.

It is an object of the present invention to provide a method for producing a drying oil-modified phenolic resole resin laminate which is excellent in low-temperature punching workability, has no deterioration in solvent resistance or white spots, and does not make the laminate opaque.

(Means for Solving Problems) In the present invention, a predetermined number of base materials impregnated with a drying oil-modified phenolic resole resin mixed with an unsaturated polyester resin having one or more double bonds in one molecule are stacked. It is a method for manufacturing a laminated plate, which is characterized by combined heating and pressing.

The unsaturated polyester resin has an α, β- having a double bond.
It is produced by reacting an unsaturated dibasic acid with glycols.

Examples of the raw material of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, citraconic acid and itaconic acid.

In order to increase flexibility, higher fatty acids such as adipic acid, azelaic acid, sebacic acid and dimer acid are used, and if necessary, polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride and dimethyl terephthalic acid are used. Acid, hexahydrophthalic acid, hexahydrophthalic anhydride, etc. may be used.

Examples of raw materials for glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and hexanediol.

The reaction temperature of α, β-unsaturated dibasic acid and glycols is
It is normally synthesized at 130 ° C to 280 ° C.

Regarding the average molecular weight of the unsaturated polyester resin, the flexibility increases as the molecular weight increases, but if the average molecular weight is 12,000 or more, the compatibility with the phenol resin decreases. Therefore, the average molecular weight of 1000 to 8000 is particularly preferable.

The unsaturated polyester resin having one or more double bonds in one molecule is contained in an amount of 3 to 120 parts, preferably 7 to 50 parts, based on 100 parts by weight of the drying oil-modified phenolic resole resin. Good part. If it is more than 120 parts, the interlaminar adhesion of the molded laminate will be reduced, and peeling and whitening will be likely to occur in the punching process. Dry oil-modified phenolic resole resin containing this unsaturated polyester resin is made into a varnish using a solvent such as toluene, alcohol, methyl ethyl ketone, acetone, styrene, etc., and heat-cured for paper, glass cloth, glass non-woven fabric, synthetic fiber cloth, etc. A predetermined amount is impregnated and adhered to the fiber base material of the functional resin laminated plate and heated and pressed to form a laminated plate.

Comparative Example 1 Maleic anhydride (490 g), adipic acid (730 g) and ethylene glycol (682 g) were placed in two reaction vessels, tetrabutyl zirconate was used as a catalyst, and the reaction was continued at 220 ° C. for 10 hours to give a molecular weight of 3
500 (polystyrene conversion value by liquid chromatography) unsaturated polyester resin was obtained. The average number of double bonds was 3.7, and the acid value was 20.

108 g of meta-cresol and 55 g of 80% paraformaldehyde were mixed and resolized under an alkaline catalyst. 20 parts of the polyester resin shown above was added to 100 parts of this phenol resin (solid content, parts by weight, the same applies hereinafter) to form an impregnating varnish, which was previously treated with a water-soluble phenol resin (resin adhesion amount: 11%). This prepreg 5
Combine the sheets with the copper foil with adhesive and heat and pressure laminate 1.
A 6 mm single-sided copper clad laminate was obtained. The characteristics of the copper clad laminate are shown in the attached table.

Example 1 Tung oil and metacresol were reacted under an acidic catalyst, and then 100 parts of a resolized resin having a modified amount of tung oil of 25%, which was resolized with paraformaldehyde and an alkaline catalyst, was mixed with 20 parts of the polyester resin synthesized in Comparative Example 1. Added to give an impregnated varnish. A copper clad laminate was obtained in the same manner as in Comparative Example 1 below.
The characteristics of the copper clad laminate are shown in the attached table.

Comparative Example 2 Using the phenol resin varnish shown in Comparative Example 1, a copper clad laminate was obtained in the same manner as in Comparative Example 1. The characteristics of the copper clad laminate are shown in the attached table.

Comparative Example 3 Using the tung oil-modified phenolic resin varnish shown in Example 1, a copper clad laminate was obtained in the same manner as in Comparative Example 1. The characteristics of the copper clad laminate are shown in the attached table.

Comparative Example 4 Tung oil and metacresol were reacted under an acidic catalyst, and then resolized with paraformaldehyde and an alkali catalyst to obtain a resolized resin with a modified amount of tung oil of 37.5%. A copper clad laminate was obtained by the same method. The characteristics of the copper clad laminate are shown in the attached table.

(Effect of the invention) By using a resin obtained by containing an unsaturated polyester resin in a drying oil-modified phenolic resole resin in the production of a laminated board, the formed laminated board can be punched well at low temperature, Accuracy improved.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takeshi Kawai 1500 Ogawa, Shimodate, Ibaraki Prefecture Shimodate Factory, Hitachi Chemical Co., Ltd. Seisaku Kogyo Co., Ltd. Yamazaki Plant (56) Reference JP 54-76671 (JP, A) JP 54-116050 (JP, A) JP 49-24272 (JP, A) JP 59- 182816 (JP, A)

Claims (1)

[Claims] 1. A method of stacking a predetermined number of base materials impregnated with a drying oil-modified phenolic resole resin containing an unsaturated polyester resin having one or more double bonds in one molecule and heating and pressing the base material. Laminated board manufacturing method.