JPS6136359A - Flame-retardant thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by incorporating a flame retardant prepared from a specific phosphorus compound and a polyhydric alcohol or polyhydric phenol is a specific amount with a thermosetting resin, having, improved heat and solvent resistance, and useful for electricalf and electronic parts having high degree of flame retardancy, etc. CONSTITUTION:A flame-retardant thermosetting resin composition obtained by incorporating 100pts.wt. thermosetting resin, e.g. phenolic resin or epoxy resin, with 5-100pts.wt., preferably 10-70pts.wt. flame retardant prepared by reacting an organic phosphorus compound expressed by the formula (X is halogen; R is H or 1-12C alkyl or alkenyl) with a polyhydric alcohol, e.g. ethylene glycol or propylene glycol, or polyhydric phenol, e.g. hydroquinone or resorcin, having two or more hydroxyl groups in one molecule. The compound expressed by the formula is easily obtained by reacting a phosphorus oxyhalide with an alkyl- or alkenylphenol or phenol.

Description

[Detailed description of the invention] [Object of the invention] Industrial field of application The present invention relates to a flame-retardant thermosetting resin composition using a phosphoric acid ester. The present invention relates to a thermosetting resin composition having properties.

Conventional technology Conventionally, in order to impart flame retardancy to thermosetting resin compositions, additive or reactive compounds such as organic phosphorus compounds, organic halogen compounds, antimony dioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, etc. have been used. A method is known in which thermosetting plum fat contains one or more types of flame retardants. In particular, organic phosphorus compounds are particularly effective in making oxygen-containing thermosetting resins flame retardant, such as phenol resins, epoxy resins, polyurethanes, and polyesters. However, conventional organophosphorus compounds,
For example, triphenyl phosphate, cresyl diphenyl phosphate, and trisdichloropropyl phosphate are effective in flame retardation to a certain extent, but ζ
It has drawbacks such as decreased heat resistance, decreased dimensional stability, and volatilization and oozing of organic phosphorus compounds under high temperature conditions.

Problem 6 to be solved by the invention A thermosetting resin obtained by reacting an organic phosphorus compound represented by the general formula [1] with a polyhydric alcohol or polyhydric phenol having two or more hydroxyl groups in one molecule. To improve the heat resistance and solvent resistance of the thermosetting resin and impart an excellent high degree of flame retardancy.

[Structure of the Invention] Means for Solving the Problems As a result of intensive research in order to solve the above drawbacks, the inventor found that the general formula <Q-o+;-x<where X is a halogen atom and R is a hydrogen atom or an alkyl group or alkenyl group having 1 to 12 carbon atoms) and a polyhydric alcohol or polyhydric phenol having two or more hydroxyl groups in one molecule. 6 to 100 parts of at least one type per 100 parts by weight of thermosetting resin
It has been found that a thermosetting resin and lI composition having excellent heat resistance, solvent resistance and high flammability can be obtained by blending parts by weight, and the present invention has been completed.

The polyhydric alcohols used in the present invention include ethylene glycol and propylene glycol.

Dihydric alcohols such as butanediol, neopentyl glycol, hexamethylene glycol, diethylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, tris(2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol One or more types of alcohols having a valence of 4 or more may be used. On the other hand, examples of polyhydric phenols include one or more of dihydric phenols such as hydroquino, resorcinol, catechol, bisphenol A, and bisphenol F, and trihydric phenols such as birogal.

Examples of the thermosetting resin used in the present invention include various thermosetting resins such as phenol resin, -boxy resin, unsaturated polyester, alkyd resin, amino resin, diallyl phthalate resin, and polyurethane.

The phosphoric acid ester may be incorporated into the thermosetting resin composition by simply adding and mixing it, depending on the properties of the thermosetting resin, or by using it as a component of the resin reaction. . If the content is less than 5 parts by weight per 100 parts by weight of resin, the flame retardant effect will not be exhibited, and if it is more than 100 parts by weight, the properties of the resin will be lost. Therefore, the content is preferably 5 to 100 parts by weight, and more preferably 10 to 70 parts by weight. section gives the most favorable results. The thermosetting resin composition in the present invention may be various modified resins, or may be combined with other flame retardants and flame retardant aids such as organic halogen-containing compounds, organic nitrogen-containing compounds, and collector compounds. Furthermore, the flame retardant effect can be improved.

The flame-retardant thermosetting resin composition of the present invention is useful for various thermosetting plum oil products, and is particularly useful for electrical and electronic components, laminates, and copper-clad laminates for printed wiring. It is useful for

Hereinafter, examples will be shown taking a laminate for electric and electronic components as an example, but the present invention is not limited to these examples.

Effect [The organic phosphorus compound represented by formula 11 is prepared by combining oxybalfugen 41-phosphorus (0=P-X, where X represents a halogen atom) and alkyl or alkenylphenol or phenol (9- OH: where R represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 12 carbon atoms), and is used as it is or after purification if necessary. As a method for producing a novel phosphoric acid ester in the present invention, the compound [1
1 and polyhydric alcohol or polyhydric phenol in a predetermined molar ratio using a brush solvent or an inert solvent, and using a common catalyst such as AlCl as a catalyst, at room temperature to 2.
The reaction is carried out at 00°C. After the reaction is complete, wash with water, medium
1. Through purification methods such as filtration, phosphoric acid ester is obtained.

Synthesis Example 1 22 g (0.2 mol) of resorcin, 100 ml of xylene, and 0.1 g of aluminum chloride were collected in a Mitsuro flask equipped with a stirrer (300 ml), and 1-54 g (0,2 mol) of diphenyl monochlorophosphate was added to this. 2 mol) was added dropwise, and the reaction was continued for an additional 4 hours under reflux. Wash this with water,
After performing purification methods such as neutralization, distillation was carried out under reduced pressure to remove the solvent to obtain sample No. 1. Phosphorus content is 9.1%
Met.

Synthesis Example 2 Using the apparatus of Synthesis Example 1, tris(2-hydroxyethyl)isocyanurate-h26> (0°1 mol), 14 g of pyridine, and 50 ml of toluene were collected. To this, 54 g (0,2
mol) was added dropwise, and the reaction was continued for 60 minutes at room temperature. After performing purification methods such as washing with water and neutralization, distillation was carried out under reduced pressure to remove the solvent to obtain 'C Sample No. 2. The phosphorus content is 8
．． It was 6%.

Synthesis example 3: (+)? (0.2 mol), 0.1 g of aluminum chloride was collected, and 19 g of phenol (
After adding 0.4 mol) little by little, the reaction was continued for 60 minutes at 11O to prepare diphenyl monochlorophosphate. To this was added a mixture of 50 ml of xylene and 27 g (0.2 mol) of trinotyrolbroban. In addition,
The reaction was continued for an additional 3 hours under reflux. After performing purification methods such as washing with water and neutralization, the sample No. 3 was obtained by distilling under reduced pressure to remove the solvent. The phosphorus content was 10.5%.

Example 1 30 parts by weight of sample No. 1 was mixed with 143 parts by weight (100 parts by weight based on solid content) of a 70 wt% methanol/acetone (171 weight ratio) solution of phenol resin (manufactured by Showa Union Gosei Co., Ltd., BLSA-3122) and fT. This was then impregnated into linter paper (YBS-10, manufactured by Chongyo Kokusaku Valve Co., Ltd.) and dried to obtain a B-stage resin-impregnated paper with a resin content of 55%. Eight sheets of this were laminated and pressed at a temperature of 150'U and a pressure of 100 kg/cm for 60 minutes to harden the resin, and then cut into plate-like pieces to obtain a phenolic resin laminate with a thickness of 1.6 mm. Ta.

The properties of this laminate are shown in Table IIZ.

Example 2 A phenolic resin laminate was obtained in the same manner as in Example 1 except that Sample No. 2 was replaced with Sample No. 001. The properties of this laminate are shown in Table 1.

Example 3 A phenolic resin laminate similar to Example 1 was obtained by replacing sample No. 3 with sample No. 1. The properties of this laminate are shown in Table 1.

Example 4 Sample No. 1 100 parts by weight, 200 parts by weight of epoxy resin (manufactured by Shell Co., Ltd., Epicoat #1001), 50 parts by weight of brominated epoxy resin (manufactured by Dow Company, DER511),
A glass cloth (180x/m 2 ) was impregnated with an epoxy resin solution consisting of 11 parts by weight of dicyandiamide and 0.4 parts by weight of benzyldimethylamine to obtain a prepreg with a resin content of 1136%. This was heated and pressed in the same manner as in Example 1 to obtain an epoxy resin laminate. The properties of this laminate are shown in Table 1.

Example 5 An epoxy resin laminate was obtained in the same manner as in Examples 1 to 14 except that Sample No. 2 was replaced with Sample No. 2.

The properties of this laminate are shown in Table 1.

Comparative Example 1 Rimple N+), 1 was replaced by cresyl diphenyl phosphate-1
・; After cooling, a phenolic resin laminate was obtained in the same manner as in Example 1. The properties of this laminate are shown in Table 1.

Comparative Example 2 Sample No. 1 was replaced with tricresyl phosphate to obtain an epoxy resin laminate in the same manner as in Example 4, and the properties of this laminate are shown in Table 1.

As can be seen from Table 1, it can be seen that when the composition of the present invention is used, it has superior shell resistance, solder resistance, and solvent resistance compared to conventional compositions.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] (In the formula, X is a halogen atom, R is a hydrogen atom, or has 1 carbon atom
At least one kind of flame retardant obtained by reacting an organophosphorus compound represented by 12 alkyl or alkenyl groups with a polyhydric alcohol or polyhydric phenol having two or more hydroxyl groups in one molecule is heated. Curable resin 10
A flame-retardant thermosetting resin composition containing 5 to 100 parts by weight relative to 0 parts by weight.