JP2002069313A - Stable flame-retarded synthetic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable flame-retarded synthetic resin composition giving a molded article having excellent stability, flame-retardance, transparency and electric properties. SOLUTION: The stable flame-retarded synthetic resin composition contains an organic phosphorus compound expressed by general formula (1) (X1 to X8 are each H, an alkyl or the like; and A is H, dihydroxyphenyl, dihydroxynaphthyl or the like) and has a organic acid compound content of <=0.2%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stable flame-retardant synthetic resin composition.
The present invention relates to a stable flame-retardant synthetic resin composition containing an organic phosphorus compound having a specific structure.

[0002]

2. Description of the Related Art Synthetic resins are widely used as moldings and coating materials utilizing their good physical and chemical properties, and are widely used. Is also important. Conventionally, an organic polyhalogenated compound such as polybromobisphenol A, polybromodiphenyl ether or the like, and antimony trioxide or the like as a concomitant agent have been used as a flame retardant for a synthetic resin molded product. In such a case, it is necessary to use a considerable amount of a flame retardant to satisfy the flame retardancy,
In addition, there is a problem in terms of molding processing, deterioration of physical properties of molded articles, and the like, and the danger of generating hydrogen halide and generating halogenated dibenzodioxin (dibenzofuran) at the time of fire. Therefore, a synthetic resin that satisfies the requirement of flame retardancy without using a halogen-based flame retardant has been demanded. Proposals have been made for the use of aluminum oxide and / or ammonium polyphosphate or red phosphorus. I have. However, these addition-type flame retardants require a relatively large amount to be added, so that it is difficult to solve the problem of deteriorating the physical properties of the molded product as described above. There is also a concern that phosphine gas will be generated during combustion of red phosphorus.

In order to cope with such a problem, it has been proposed to incorporate an organic phosphorus compound represented by the structural formulas (1-1) to (1-3) into a synthetic resin (JP-A-49-351). , Japanese Patent Publication No. 48-40100, Japanese Patent Publication No. 61-
36870, Japanese Patent Publication 1-50712, Japanese Patent Publication 4-538
74 publications).

[0004]

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[0005]

However, the compound represented by the structural formula (1-1) (hereinafter referred to as HCA)
Is obtained, for example, by heat-condensing o-phenylphenol and phosphorus trichloride in the presence of a zinc chloride catalyst, hydrolyzing in an aqueous solution of sodium hydroxide, sulfate precipitation, filtration and dehydration ring closure (Japanese Patent Publication No. 49-1979). No. 45397, Special Publication No. 50-
17979). 100 ° C during these manufacturing processes
, The resulting HCA contains significant amounts of organic acid compounds such as o-2'-hydroxy-biphenyl-hydrogen-phosphinic acid, 9-hydroxy-
10-hydro-10-oxa-9-phosphaphenanthrene-9-oxide is formed. The content of these organic acid compounds is about 2 to 3%, but it has been found that even when blended with a synthetic resin as a stabilizer flame retardant, it has a considerable effect on the physical and chemical properties of the obtained molded product. . In particular,
This is important when a synthetic resin is required to have transparency, electrical characteristics, adhesion to other materials, and the like.

It is an object of the present invention to provide a synthetic resin molded product, particularly a molded product for electric parts and electronic equipment parts, which has good stability, flame retardancy, and has satisfactory physical and chemical properties. An object of the present invention is to provide a stable flame-retardant resin composition which can be easily and inexpensively manufactured.

[0007]

That is, the present invention provides a compound represented by the following general formula (1):

[0008]

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[In the general formula (1), X ₁ to X ₈ are the same or different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and A represents a hydrogen atom or an alkyl group, a cycloalkyl group; A dihydroxyphenyl group or a dihydroxynaphthyl group which may be substituted with a group, an aryl group or an aralkyl group. In the stable flame-retardant synthetic resin composition containing an organic phosphorus compound represented by the formula (1), the content of the organic acid compound in the synthetic resin composition is 0.2% or less, preferably 0.05% or less. Which is a stable flame-retardant synthetic resin composition.

Further, the present invention provides a stable flame-retardant synthetic resin composition containing an organic phosphorus compound represented by the above general formula (1), wherein the content of the organic acid compound is as said organic phosphorus compound. 1.0% or less, preferably 0.3%
A stable flame-retardant synthetic resin composition characterized by using the following:

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the organophosphorus compound represented by the general formula (1), X _{1 to} X ₈ =
_{H; X 2 = X 6 =} X 8 = CH 3; X 6 = t- butyl,
α, α-dimethylbenzyl; X ₈ = cyclohexyl, phenyl (all other X _i is H); A = 1,
4-dihydroxyphenyl-2-yl, 1,4-dihydroxy-5- (t-butyl, cyclohexyl or phenyl) phenyl-2-yl, 1,4-dihydroxynaphthyl-2-yl, 1,4-dihydroxynaphthyl- Compounds represented by 6-methyl-2-yl and the like, and particularly preferred are compounds represented by the above structural formulas (1-1) (hereinafter referred to as HCA) to structural formulas (1-3).

The compound represented by the structural formula (1-2, hereinafter abbreviated as P-HQ) or (1-3, hereinafter abbreviated as P-NQ) is the same as the compound of the structural formula (1-1). It can be obtained by reacting a molar ratio of 1,4-benzoquinone or 1,4-naphthoquinone in an inert organic solvent (for example, Japanese Patent Publication No. 1-50712).

As a method for producing the organic phosphorus compound represented by the structural formula (1-1) according to the present invention, the following method is exemplified.

(I) A compound represented by the structural formula (a) obtained by heating and reacting biphenyl with phosphorus trichloride in the presence of a catalyst is hydrolyzed in an aqueous sodium hydroxide solution, and then acid-precipitated with sulfuric acid. The compound of the structural formula (b) precipitated by filtration, washed with water, and dehydrated with heating at 130 ° C. to obtain HCA-A having the quality level shown in Table 1 below (JP-B-49-45397, JP-B-50). 17979, each gazette).

(Ii) The precipitate obtained by the acid precipitation in the above (i) is filtered, washed with water, and then reacted by lowering the temperature in the above-mentioned step of heating and dehydrating the ring to 130 ° C. to 120 ° C. HCA-B of the indicated quality level is obtained.

After the filtration and washing with water, the air is shut off and the ring is heated and dehydrated in a nitrogen atmosphere to obtain HCA-C having a quality level shown in Table 1 below.

[0017]

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In Table 1 below, P-HQ-A is HCA
-A, and P-HQ-B, HCA-B, P-HQ
-C is obtained by reacting HCA-C with 1,4-benzoquinone by heating in an inert organic solvent (eg, ethyl cellosolve) as a raw material (Japanese Patent Publication No. 1-5071).
No. 2).

The amount of the synthetic resin according to the present invention that satisfies the stability and flame retardancy is appropriately selected depending on the kind of the synthetic resin, the properties to be imparted, and the like. Parts, the same shall apply hereinafter) of the organic phosphorus compound in an amount of 0.5 to 25 parts, preferably about 1 to 20 parts, and the phosphorus atom content in the flame-retardant epoxy resin composition is 0.5 to 15% (% by weight). The same applies hereinafter), preferably about 1 to 10%.

Examples of the transparent resin include epoxy resins, polyolefin resins such as polypropylene, polystyrene resins, acrylonitrile-butadiene-styrene copolymer resins, acrylonitrile-styrene copolymer resins, methacrylic acid-styrene copolymer resins, methacrylic resins, styrene Butadiene copolymer resin, polycarbonate resin, polyamide resin, polyarylate resin, polyacrylate resin, polysulfone resin, polyallyl sulfone resin, polyether sulfone resin, polyetherimide resin, polyimide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene -Ter resin, bis-maleimide-triazine resin, polyester carbonate resin or alloy resin thereof, and the like.

As the epoxy resin, a known epoxy resin such as a diglycidyl ether compound such as bisphenol A, bisphenol F, bisphenol S, phenol novolak or orthocresol novolac, or a tetraglycidyl compound such as diaminodiphenylmethane or diaminodiphenylsulfone is used alone. Alternatively, they can be used in combination. Examples of the curing agent include organic acid anhydrides, polyamine-based compounds, phenol-based compounds and the like which are usually used.

The organic phosphorus compound according to the present invention is not only the compound represented by the general formula (1) itself, but also a compound derived therefrom, for example, the structural formula (2) or its anhydride, or the general formula (3)

[0023]

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[In the general formula (3), R represents a hydrogen atom or a methyl group, and m and n each represent an integer of 1 or more. The same applies to the use of a compound represented by the formula

The organic acid compound according to the present invention includes o-2'-hydroxy-biphenyl-hydrogen-phosphinic acid of the following formula (B) and 9-hydroxy-10-hydro-10-oxa of the following formula (C). And -9-phosphaphenanthrene-9-oxide.

[0026]

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[0027]

Next, an embodiment of the present invention will be described.

Table 1 shows the quality of HCA and P-HQ used.
As shown in FIG.

The amount of the organic acid compound in the organic phosphorus compound is
The organophosphorus compound was dissolved in ethanol and measured by liquid column chromatography. The measurement conditions of the liquid chromatography were as follows: Silica gel was 4.6 mmφ × 25 c
m, and the eluent (hexane / ethanol /
Acetic acid / ammonium acetate = 750/250/10/5 parts by weight) at 1.0 ml / min. And separated.

Retention time 10.0 min. The peak of the organic acid compound (C) showed a retention time of 14.0.
min. Have peaks of HCA and the organic acid compound (B).

The identification of the organic acid compound (C) was carried out by fractionating a peak of the organic acid compound (C) by preparative liquid column chromatography and performing infrared analysis, H-NMR and melting point measurement.
The organic acid compound (C) was quantified with a calibration curve, and the results shown in Table 1 were obtained.

Regarding the analysis of HCA and the organic acid compound (B), the peaks were overlapped by liquid chromatography, and identification and quantification could not be performed. Therefore, a sample for preparing a calibration curve, in which the organic acid compound (B) was added to HCA in amounts up to 5% in advance, was subjected to DSC under nitrogen atmosphere.
The measurement was performed, and a calibration curve was prepared from a peak due to dehydration of the organic acid compound (B), and the organic acid compound (B) was prepared from both components fractionated by preparative liquid column chromatography using this calibration curve. Was measured, and the results shown in Table 1 were obtained.

[0033]

[Table 1]

Example 1, Comparative Example 1 HCA1 was added to 100 parts of an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) (Psycolac GS: Ube Sycon).
0 parts, 0.5 parts of dilauryl thiodipropionate and 0.5 parts of a bisphenol-based antioxidant were mixed, and pellets were prepared using a Banbury mixer and a roll mill, and tested with a screw type injection molding machine. A piece was prepared, and the total light transmittance was measured according to the method of ASTM-D-1003. Table 2 shows the results.

[0035]

[Table 2]

Example 2, Comparative Example 2 Polyethylene terephthalate resin (TR1400BH: Teijin Limited) 100
, 15 parts of HCA and 0.1 part of an antioxidant (Irganox: Ciba-Geigy) were mixed to prepare a test piece in the same manner as in Example 1, and the total light transmittance was measured. Table 3 shows the results.

[0037]

[Table 3]

Example 3, Comparative Example 3 100 parts of an epoxy resin (epoxy equivalent: 190, Epicoat 828: Shell Sekiyu KK), 30 parts of P-HQ, and 0.1 part of tetramethylammonium chloride were mixed and melted to obtain a mixture of 120 parts. 5 at ℃
After reacting for 20 hours, 20 parts of 4,4'-diaminodiphenylmethane was added thereto, and the mixture was cured at 150 ° C. for 5 hours to prepare a test piece. Similarly, the total light transmittance and dielectric constant (JISK
6911) was measured. Table 4 shows the results.

[0039]

[Table 4]

[0040]

As described above, in the synthetic flame-retardant synthetic resin composition containing the organophosphorus compound represented by the general formula (1), the content of the organic acid compound in the organophosphorus compound to be contained is 1.0 to 1.0. % Or less, particularly by regulating the content of the organic acid compound in the synthetic resin composition to be 0.2% or less, whereby the physical and chemical properties of the resulting synthetic resin molded product are controlled. The properties, especially the transparency and electrical properties of the molded product, are excellent.

Continuing from the front page (72) Inventor Hiroshi Sumitomo 1-10-24, Itikaichi, Ibaraki-shi, Osaka F-term (reference) 4M028 AA35 AA42 AA44 BA06 4H050 AA03 AB80 4J002 AC081 BB121 BC031 BC061 BC071 BG021 BG061 BN151 CA001 CD051 CD061 CF061 CF071 CF161 CG001 CH071 CL001 CM041 CM051 CN031 EW136 FD136

Claims (5)

[Claims] 1. A compound of the general formula (1) [In the general formula (1), X ₁ to X ₈ are the same or different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and A represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group. Represents a dihydroxyphenyl group or a dihydroxynaphthyl group which may be substituted with a group or an aralkyl group. In the stable flame-retardant synthetic resin composition containing an organophosphorus compound represented by the formula (1), the content of the organic acid compound in the synthetic resin composition is 0.2
% Or less, a stable flame-retardant synthetic resin composition. 2. A compound of the general formula (1) [In the general formula (1), X ₁ to X ₈ are the same or different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and A represents a hydrogen atom or an alkyl group, a cycloalkyl group, an aryl group. Represents a dihydroxyphenyl group or a dihydroxynaphthyl group which may be substituted with a group or an aralkyl group. ] In the stable flame-retardant synthetic resin composition containing an organic phosphorus compound represented by formula (1), a compound having an organic acid compound content of 1.0% or less is used as the organic phosphorus compound to be contained. And a stable flame-retardant synthetic resin composition. 3. The stability according to claim 1, wherein the organophosphorus compound represented by the general formula (1) is one represented by a structural formula (1-1) to a structural formula (1-3). Flame-retardant synthetic resin composition. Embedded image 4. A synthetic resin containing an organic phosphorus compound represented by the general formula (1) is an epoxy resin, a polyolefin resin, a polycarbonate resin, a polystyrene resin, an acrylonitrile / butadiene / styrene copolymer resin, an acrylonitrile / styrene copolymer resin, Polyamide resin, polyarylate resin, polyacrylate resin, polysulfone resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenyl ether resin,
The stable flame-retardant synthetic resin composition according to any one of claims 1 to 3, which is a bis-maleimide-triazine resin or an alloy resin thereof. 5. The organic acid compound contained is o-2′-hydroxy-biphenyl-hydrogen-phosphinic acid of the following formula (B), 9-hydroxy-10-hydro-10- of the following formula (C): The stable flame-retardant synthetic resin composition according to any one of claims 1 to 4, which is at least one selected from oxa-9-phosphaphenanthrene-9-oxide. Embedded image