JPH0764937B2 - 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 laminate having excellent flame retardancy and punching workability.

(Prior Art) With the recent remarkable development of the electronic equipment industry, the density of electronic equipment has increased, and from the viewpoint of safety, the demand for heat resistance of laminated boards for printed wiring boards has become more stringent. Laws and standards such as US UL standards have been established, and their regulations are being strengthened. In addition, recently, with the increasing density of printed wiring boards used in electronic devices, automatic packaging technology has also advanced, and stricter dimensional accuracy is required. To meet this requirement, low-temperature punching is being performed. ing.

Conventionally, in order to improve punching workability, plasticizers such as phosphoric acid esters and polyethers have been added to thermosetting resins, or thermosetting resins with thermosetting resins such as drying oils and polybutadienes. The resin is modified by the reaction of the resin.

On the other hand, flame-retardant methods for thermosetting resins are phosphorus compounds such as phosphoric acid esters, brominated phenols, brominated epokin compounds, brominated compounds such as brominated biphenyl ethers, and nitrogen-based compounds such as triazine compounds. The compound and the inorganic compound such as antimony are used alone or in combination to add heat resistance to the thermosetting resin.

(Problems to be Solved by the Invention) As the punching temperature is lowered, it is necessary to further increase the amount of the plasticizer. This causes a decrease in the crosslink density of the thermosetting resin, which leads to the punching processability. Causes marked bulges around the punched holes and significantly reduces heat resistance and solvent resistance. Further, in order to impart flame retardancy, it is necessary to add a larger amount of flame retardant, and the punching processability, heat resistance, and solvent resistance are significantly deteriorated. Further, there is a problem of compatibility between the plasticizer and the flame retardant to be used, and it is difficult to balance the amount of the plasticizer with the amount of the flame retardant because the characteristics vary due to the non-uniform curing reaction.

The present invention provides a method for producing a laminated plate having excellent flame retardancy and punching processability at the same time.

(Means for Solving the Problems) The present invention is a group obtained by impregnating a varnish prepared by mixing a bromine-containing unsaturated polyester resin having a double bond in the molecule with a drying oil-modified phenolic resole resin in a predetermined amount and adhering the varnish. The material is formed by molding.

Examples of the unsaturated polyester resin shown above include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, and other α, β unsaturated dibasic acids having a double bond, and glycols are ethylene glycol and diethylene glycol. Bromine-containing compounds such as triethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, and hexanediol are tetrabromophthalic anhydride, dibromoneopentyl glycol, tribromoallyl alcohol, or tetrabromobisphenol A diglycidyl. Compounds that increase flexibility such as bromine-containing epoxy compounds such as ethers include adipic acid, azelaic acid, higher fatty acids such as sebacic acid and dimer acid, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, etc. Using polybasic acids such as taric acid, phthalic anhydride, dimethyl terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, reaction temperature 80-280 ° C
Is synthesized by.

Bromine-containing unsaturated polyester resin has a bromine content of 5% to
40% is preferable, and a high bromine content may reduce flexibility. Further, the average molecular weight of the bromine-containing unsaturated polyester resin is preferably 1000 to 12000, the flexibility increases as the molecular weight increases, but compatibility with the drying oil-modified phenolic resole resin to be blended when the average molecular weight is 17,000 or more. May decrease.

Dry oils such as tung oil, dehydrated castor oil, and deer oil are used.Phenolic phenols include phenol, metacresol, paracresol, orthocresol, paraisopropylphenol, paratertiarybutylphenol, paraisopropenyl. Oligomers of phenol, nonylphenol, bisphenol A and the like are used. Further, since it is a polyester resin having a double bond, the compatibility with the drying oil-modified phenolic resole resin is not lowered, and the characteristics when it is used as a laminated board are stable.

The blending amount of the bromine-containing unsaturated polyester resin having a double bond in the molecule is a drying oil-modified phenolic resole resin.
It is contained in an amount of 3 to 120 parts per 100 parts (the same applies hereafter by weight), but preferably 5 to 50 parts. If it is more than 120 parts, the interlayer adhesion of the formed laminate will be deteriorated, and peeling and whitening will be likely to occur in the punching process. A solvent such as toluene, alcohol, methyl ethyl ketone, acetone, dimethylformamide, styrene, etc. is used for the dry oil-modified phenolic resole resin containing this bromine-containing unsaturated polyester resin to form a varnish, paper, glass cloth, glass non-woven fabric, synthetic fiber. A predetermined amount is impregnated and adhered to an ordinary base material of a thermosetting resin laminated plate such as cloth to obtain a molded laminated plate.

Molding is carried out at the required temperature and the required pressure (including no pressure) with one sheet of the base material impregnated with the drying oil-modified phenolic resole resin varnish mixed with the bromine-containing unsaturated polyester resin or the necessary number of superposed layers. . Also, as auxiliary flame retardants, phosphoric acid esters such as triphenyl phosphate, cresyl diphenyl phosphate, isopropyl phenyl diphenyl phosphate, tetrabromobisphenol A, brominated epoxy compounds, brominated biphenyl ether compounds, etc. You may use the bromine compound of.

(Function) The bromine-containing unsaturated polyester resin having a double bond in the molecule reacts with the compatible drying oil-modified phenolic resole resin and becomes a part of the matrix. Then, bromine acts as a flame retardant, and the long-chain structure of the unsaturated polyester gives the matrix flexibility. As a result of giving flexibility to the matrix, punching workability is improved.

Example 1. Maleic anhydride 490 g, tetrabromophthalic anhydride 696 g,
730 g of adipic acid and 744 g of ethylene glycol were placed in 3 reaction vessels and tetrabutyl zirconate was used as a catalyst to continue the reaction at 220 ° C. for 10 hours to obtain an unsaturated polyester resin having a bromine content of 18%. The average number of double bonds is 3 per molecule
Four of them had an acid value of 20.

Tung oil and phenol are reacted under acidic catalyst, and then 80% paraformaldehyde and resolized under alkaline catalyst are added to 100 parts of tung oil modified phenol resin of 33% modification amount, 30 parts of polyester resin synthesized above, tetrabromo 5 parts of bisphenol A and 30 parts of triphenyl phosphate were mixed to prepare a varnish for impregnation. Treated with a water-soluble melamine-modified phenolic resin in advance (resin coverage 19-23%),
The above-mentioned impregnating varnish on the craft base is 58-60%
Was impregnated and dried, and 6 sheets of this prepreg and a copper foil with an adhesive were combined and laminated under heat and pressure to obtain a 1.6 mm single-sided copper clad laminate.

The characteristics of the copper clad laminate are shown in the attached table.

Comparative Example 1. 94 g of phenol and 55 g of 80% paraformaldehyde were mixed and resolized under an alkali catalyst to obtain a phenol resin. 14 parts of tetrabromobisphenol A and 30 parts of toluphenyl phosphate were mixed with 100 parts of this phenol resin to obtain an impregnating varnish, and a copper clad laminate was obtained in the same manner as in Example 1 below. The characteristics of the copper clad laminate are shown in the attached table.

Comparative Example 2. 100 parts of the tung oil-modified phenolic resin shown in Example 1 was mixed with 14 parts of tetrabromobisphenol A and 30 parts of triphenyl phosphate to obtain an impregnating varnish, which was copper clad in the same manner as in Example 1 below. A laminated board was obtained. The characteristics of the copper clad laminate are shown in the attached table.

Comparative Example 3. Tung oil and phenol were reacted under an acid catalyst, and then 80% paraformaldehyde and an alkaline catalyst were resolized to 100 parts of a 48.5% tung oil modified phenol resin to 14 parts of tetrabromobisphenol and 14 parts of triphenyl. A varnish for impregnation was prepared by mixing 30 parts of phosphate. A copper clad laminate was obtained in the same manner as in the examples below. The characteristics of the copper clad laminate are shown in the attached table.

(Effects of the Invention) In the present invention, it is possible to improve the difficulty by using a bromine-containing unsaturated polyester resin having one or more double bonds in the molecule as a flame retardant plasticizer in a drying oil-modified phenolic resole resin. It is possible to produce a laminate having excellent flame resistance, punching workability, heat resistance, and solvent resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location B29K 105: 06 C08L 61:04 (72) Inventor Hanake Myoton 1500 Ogawa, Shimodate, Ibaraki Prefecture Hitachi Chemical Industrial Co., Ltd. Shimodate Plant (72) Inventor Masafumi Yano 1500 Ogawa, Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Shimodate Plant (56) Reference JP-A-57-7187 (JP, A)

Claims (1)

[Claims] 1. A base material is formed by impregnating and adhering a predetermined amount of a varnish prepared by mixing a bromine-containing unsaturated polyester resin having a double bond in the molecule with a drying oil-modified phenolic resole resin. Laminated board manufacturing method.