WO2002016501A1

WO2002016501A1 - Stably flame-retardant synthetic resin composition

Info

Publication number: WO2002016501A1
Application number: PCT/JP2000/005580
Authority: WO
Inventors: Takumi Hirayama; Hiroshi Sumitomo
Original assignee: Sanko Kaihatsu Kagaku Kenkyusho
Priority date: 1999-05-26
Filing date: 2000-08-21
Publication date: 2002-02-28
Also published as: JP2000336204A

Abstract

A stably flame-retardant synthetic resin composition which gives moldings excellent in flame-retardant stability, transparency, and electrical properties. The stably flame-retardant synthetic resin composition is a synthetic resin composition which contains an organophosphorus compound represented by the general formula (1) (wherein X1 to X8 each represents hydrogen, alkyl, etc.; and A represents hydrogen, dihydroxyphenyl, dihydroxynaphthyl, etc.) and in which the content of atoms present in an inorganic state is up to 25 ppm. The composition gives synthetic resin moldings excellent in physical and chemical properties, especially in transparency and electrical properties. (1)

Description

Description Stable flame-retardant synthetic resin composition

Technical field

The present invention relates to a stable flame-retardant synthetic resin composition, and more particularly to a stable flame-retardant synthetic resin composition containing an organic phosphorus compound having a low inorganic atom content and a specific structure.

Background art

Synthetic resins are widely used and molded as moldings and coatings utilizing their good physical and chemical properties, but their physical properties and their requirements for stability and flame retardancy are also high. It is important. Heretofore, as a flame retardant for synthetic resin molded articles, organic polyhalogenated compounds such as polybromobisphenol 8, polybromodiphenyl ether and the like, and antimony trioxide and the like as a concomitant agent have been used. In such cases, it is necessary to use a considerable amount of a flame retardant to satisfy the flame retardancy, and there is a problem in molding process, deterioration of the physical properties of molded products, and fire. The danger of halo formation at the time is inevitable. Therefore, there is a demand for a synthetic resin that satisfies the requirement of flame retardancy without using a halogen-based flame retardant, and proposals have been made to use aluminum oxide and / or ammonium polyphosphate / red phosphorus. ing. However, these addition-type flame retardants require a relatively large amount of addition, so that the problem of deteriorating the physical properties of the molded product as described above is difficult to solve. There is also concern that red phosphorus will generate phosphine gas during combustion.

In order to cope with such problems, it has been proposed that synthetic resins contain an organic phosphorus compound represented by the structural formula (1-1) or (1-3). (JP-A-49-351, JP-B-48-410009, JP-B-61-36870, JP-B-1-50712, JP-B-4-153874, etc.)

(1-1) (1-2) (1-3) However, the compound represented by the structural formula (1 _ 1) (hereinafter referred to as HCA) is, for example, a compound obtained by converting o_phenylphenol and phosphorus trichloride into zinc chloride. It is obtained by condensing under heating in the presence of a catalyst, hydrolyzing in an aqueous sodium hydroxide solution, precipitation with sulfuric acid, filtration and dehydration ring closure (JP-B-49-45397, JP-B-50-17979) ). Therefore, the resulting HC A contains a considerable amount of inorganic compounds such as zinc chloride, sodium chloride, sodium sulfate and the like. These are about 100 ppm in total as 1 atom of Zn, Na, and C. However, even when compounded with synthetic resin as a flame retardant stabilizer, they are ignored in the physical and chemical properties of the resulting molded product. It was found to have an unpredictable effect. This is particularly important when the synthetic resin requires transparency, electrical properties, and adhesion to other materials.

An object of the present invention is to provide a synthetic resin molded product, particularly a molded product for electric parts and electronic equipment parts, which has good stability and flame retardancy, and yet has satisfactory physical and chemical properties, and is technically easy to use. Another object of the present invention is to provide a stable flame-retardant resin composition which can be manufactured at low cost.

Disclosure of the invention That is, the present invention relates to the general formula (1)

[In general formula (1), to x ₈ denote identically or differently hydrogen atoms, § alkyl group, a cycloalkyl group, a Ariru group or Ararukiru group, A is a hydrogen atom or an alkyl group, a cycloalkyl group, Ariru group Or a dihydroxyphenyl group or a dihydroxynaphthyl group which may be substituted with an aralkyl group. ]

In the stable flame-retardant synthetic resin composition containing an organophosphorus compound represented by the formula, the content of inorganic atoms in the synthetic resin composition is 25 ppm or less, preferably 10 ppm or less. A stable flame-retardant synthetic resin composition characterized in that:

Further, the present invention provides a stable flame-retardant synthetic resin composition containing an organic phosphorus compound represented by the general formula (1), wherein the organic phosphorus compound contained has an inorganic atom content of 100 A stable flame-retardant synthetic resin composition characterized by using a composition having a ppm or less, preferably 50 ppm or less.

BEST MODE FOR CARRYING OUT THE INVENTION

In the organic phosphorus compound represented by the general formula (1), as preferred _{_{examples, ~X 8 = H; X 2}} = X 6 = X g = CH 3; X 6 = t- heptyl, a, shed over dimethylbenzyl; X ₈ = cyclohexyl, phenyl (all other Xi are H); A = l, 4-dihydroxyphenyl — 2 1,4-dihydroxy-5- (t-butyl,

Phenyl) phenyl-2-yl, 1,4-dihydroxynaphthyl-2-yl, 1,4-dihydroxynaphthyl-6-methyl-2-yl and the like. Particularly preferred are the compounds described above. A compound represented by the structural formula (1-1) (hereinafter referred to as HCA) or the structural formula (1-3).

The compound represented by the structural formula (112, hereinafter abbreviated as P—HQ) or (1-3, hereinafter abbreviated as P—NQ) has an equimolar ratio with the compound of the structural formula (111). It is obtained by reacting 1,4-benzoquinone or 1,4-naphthoquinone in an inert organic solvent (for example, Japanese Patent Publication No. 115071/12).

As a method for producing the organic phosphorus compound represented by the structural formula (111) according to the present invention, the following method is exemplified.

(A) The compound of the structural formula (a) obtained by heating and reacting bifur II with phosphorus trichloride in the presence of a catalyst is hydrolyzed in an aqueous sodium hydroxide solution, and then acidified with sulfuric acid. The compound of formula (b), which precipitates in prayer, is filtered, washed with water, and heated and dehydrated to give HC A-A of the quality level shown in Table 1 below (JP-B-49-45397, JP-B-50) -See 179797, each gazette).

(B) To the compound represented by the structural formula (b) obtained by acid precipitation in the above (A), add twice the amount of water, stir, heat, cool, and stand still, and separate the supernatant aqueous layer. Then, add twice the amount of water to the precipitate again and repeat the same procedure. After performing this operation a total of three times, the precipitate is filtered, washed, heated and dehydrated and closed to obtain HCA-B having the quality level shown in Table 1 below.

(C) Obtained by heating and hydrolyzing a compound represented by the structural formula (a) in the coexistence of an excess of water and an organic solvent insoluble in water and inert to the reaction system (eg, toluene). The compound represented by the structural formula (b) is separated, By heating and dehydration ring closure, HCA-P having the quality level shown in Table 1 below can be obtained (JP-A-10-1490).

In Table 1 below, PHQ-P is HCA-P, PHQ-A is HCA-A, and PHQ-B is HCA-B. In an inert organic solvent (eg, ethyl ester solvent), , 4 obtained by a thermal reaction with benzoquinone (see Japanese Patent Publication No. 115071/12).

The addition amount that satisfies the stability and flame retardancy of the synthetic resin according to the present invention is appropriately selected depending on the kind of the synthetic resin, the purpose of application, and the like. For example, in the case of a transparent resin, 100 parts (parts by weight, The same) per 0.5 to 25 parts, preferably about 1 to 20 parts of an organic phosphorus compound, and the content of phosphorus atoms in the flame-retardant epoxy resin composition is 0.5 to 15% (% by weight or less). Same), preferably about 1 to 10%.

Transparent resins include epoxy resins, polyolefin resins such as polypropylene, polystyrene resins, polystyrene resins, acrylonitrile 'butadiene' styrene copolymer resin, acrylonitrile 'styrene copolymer resin, methacrylic acid' styrene copolymer resin, methacryl resin, 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, polyester resin, polyphenyl ether resin, bismale Examples thereof include imido-triazine resins and alloy resins thereof.

Known epoxy resins include diglycidyl ether compounds such as bisphenol A, bisphenol F, bisphenol S, phenol nopolak, and orthocresol novolac, and tetradaricidyl compounds such as diaminodiphenylmethane and diaminodiphenylsulfone. Epoxy resins can be used alone or as a mixture. Examples of the curing agent include those usually used, such as organic acid anhydrides, polyamine compounds, and phenol compounds.

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

CH ₂ -CO0H

( twenty three )

[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 (1) for a synthetic resin.

Next, examples of the present invention will be described.

The quality of HCA and P-HQ used is as shown in Table 1. Purity of general formula (1) C% J Inorganic element content (PPm)

Compound type

Z n Na C 1 S 0,

HCA

H C A-P 99. 9 1 1 1 <1

HCA- A 99.8 7 200 1 00 <1

HCA-B 99.8 3 50 35 <1

P-HQ

P— H Q— P 99.8 <1 <1 <1 <1

P-HQ-A 99.8 5 150 80 <1

P-HQ-B 99. 8 2 40 25 <1

[Example 1, Comparative Example 1]

Acrylonitrile 'butadiene / styrene copolymer resin (ABS resin)

(Psycolac GS: Ube Sycon Co., Ltd.) Mix 100 parts of HCA 8 parts, 0.5 parts of dilauryl thiodipropionate and 0.5 parts of a bisphenol-based antioxidant, and use a Banbury mixer and a roll mill. A pellet was prepared, and a test piece was prepared from the pellet using a screw-type injection molding machine, and the total light transmittance was measured according to the method of ASTM-D-1003. The results are shown in Table 2.

Table 2

[Example 2, Comparative Example 2]

100 parts of polyethylene terephthalate resin (TR 1400 BH: Teijin), 8 parts of HCA and 0.1 part of an antioxidant (Ilganox: Ciba Geigy) were mixed and the test piece was prepared in the same manner as in Example 1. It was prepared and the total light transmittance was measured. The results are shown in Table 3. Table 3

[Example 3, Comparative Example 3]

Epoxy resin (epoxy equivalent: 190, Epikote 828: Shell Stone Oil Co.) 100 parts, P-HQ3 5 parts and tetramethylammonium chloride 0.1 part are mixed and melted. After reacting, add 20 parts of 4,4'-diaminodiphenylmethane and cure at 150 for 5 hours. Then, a test piece was prepared, and the total light transmittance and the dielectric constant (JISK6911) were measured in the same manner. The results are shown in Table 4. Table 4

Industrial applicability

An object of the present invention is to provide a stabilized flame-retarded synthetic resin composition containing an organic phosphorus compound represented by the general formula (1), wherein the content of inorganic atoms of the organic phosphorus compound to be contained is 10%. By using a compound having a content of 0 ppm or less, particularly by regulating the content of inorganic atoms in the synthetic resin composition to 25 ppm or less, the physical and chemical The properties, especially the transparency and electrical properties of the molded product, are excellent. In addition, synthetic resin molded products, especially molded products for electrical and electronic components, have good stability and flame retardancy, and can be manufactured technically easily and at low cost.

Claims

Claims General formula (1) A

[In general formula (1) represents X, to x ₈ denote identically or differently hydrogen atoms, § alkyl group, a cycloalkyl group, a § re Ichiru group or Ararukiru group,

A represents a hydrogen atom or a dihydroxyphenyl group or a dihydroxynaphthyl group which may be substituted with an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. ]

A stable flame-retardant synthetic resin composition containing an organophosphorus compound represented by the formula: wherein the content of inorganic atoms in the synthetic resin composition is 25 ppm or less. Flame-retardant synthetic resin composition.

2. General formula (1)

[In the general formula (1), X and X ₈ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, A represents a hydrogen atom or a dihydroxyphenyl group or a dihydroxynaphthyl group which may be substituted with an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. ]

In the stable flame-retardant synthetic resin composition containing an organophosphorus compound represented by the formula, a compound having an inorganic atom content of 100 ppm or less is used as the organophosphorus compound contained therein. A stable flame-retardant synthetic resin composition.

3. The organic phosphorus compound represented by the general formula (1) according to claim 1 or 2, wherein the organic phosphorus compound is represented by a structural formula (111) or a structural formula (113). Stable flame-retardant synthetic resin composition.

(1-1) (1-2) (1-3)

4. Synthetic resins containing the organic phosphorus compound represented by the general formula (1) are epoxy resins, polyolefin resins, polycarbonate resins, polystyrene resins, acrylonitrile / butadiene / styrene copolymer resins, and acrylonitrile / styrene copolymer resins. A polyamide resin, a polyarylate resin, a polyacrylate resin, a polysulfone resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polyphenyl ether resin, a bismaleimide-triazine resin or an alloy resin thereof. 3. The stable flame-retardant synthetic resin composition according to claim 1 or 2. Rate resin, polyphenyl ether resin, bis maleimide-triazine resin

5. The organic phosphorus compound represented by the general formula (1) is a compound represented by the structural formula (1-1-1) or the structural formula (1_3), and the organic phosphorus compound represented by the general formula (1) Synthetic resin containing epoxy resin, polyolefin resin, polycarbonate resin, polystyrene resin, acrylonitrile butadiene styrene copolymer resin, acrylonitrile styrene copolymer resin, polyamide resin, polyarylate resin, polysulfone resin, polyethylene terelev 3. The stable flame-retardant synthetic resin composition according to claim 1, which is a latex resin or an alloy resin thereof.

(1-1) (1-2) (1-3)

6. The stable flame-retardant synthetic resin composition according to claim 1 or 2, wherein the contained inorganic atom is at least one selected from Na, Zn, and C1. .

7. Synthetic resins containing organophosphorus compounds represented by general formula (1) are epoxy resins, polyolefin resins, polycarbonate resins, polystyrene resins, acrylonitrile-butadiene-styrene copolymer resins, acrylonitrile, styrene copolymer resins. , Polyamide resin, polyarylate resin, polysulfone resin, polyethylene terephthalate resin or their 3.The stable flame-retardant synthetic resin composition according to claim 1 or 2, wherein the composition is a Roy resin, and the contained inorganic atom is at least one selected from Na, Zn, and CI. .

8. The organic phosphorus compound represented by the general formula (1) is a compound represented by the structural formula (1-1) or the structural formula (113), and the organic phosphorus compound represented by the general formula (1) Synthetic resin containing epoxy resin, polyolefin resin, polyolefin resin, polystyrene resin, acrylonitrile-butene-gene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polyamide resin, polyarylate resin, poly Claim 1 or Claim 2, wherein the resin is a sulfone resin, a polyethylene terephthalate resin or an alloy resin thereof, and the contained inorganic atom is at least one selected from Na, Zn and C1. 3. The stable flame-retardant synthetic resin composition according to item 2.

(1-1) (1-2) (1-3)

9. The stable flame-retardant synthetic resin composition according to claim 1, wherein the content of inorganic atoms in the synthetic resin composition is 10 ppm or less.

10. The stable flame-retardant synthetic resin composition according to claim 2, wherein the content of inorganic atoms in the organic phosphorus compound contained in the synthetic resin composition is 50 ppm or less.