JP2002332413A - Antimony-containing flame retardant for thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antimony-containing flame retardant which is used for thermoplastic resins, has excellent flame retardancy, makes it possible to homogeneously knead the flame retardant without scattering the dust of an injurious antimony compound and can give stable mechanical characteristics to the product. SOLUTION: This antimony-containing flame retardant for the thermoplastic resins comprises 100 pts.wt. of a high mol.wt. halogen-containing epoxy modified product having a polymerization degree of >=20 and 10 to 100 pts.wt. of an antimony compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in flame retardancy, and when kneading into a thermoplastic resin, harmful dust of an antimony compound is hardly scattered. The present invention relates to a flame retardant for an antimony-containing thermoplastic resin, which can provide stable mechanical properties and flame retardancy.

[0002]

2. Description of the Related Art Thermoplastic resins have been widely used in various fields such as mechanical parts, electric parts and automobile parts in recent years, utilizing their respective characteristics. On the other hand, among these industrial materials, in particular, in the field of electric and electronic parts, the demand for fire safety has been increased, and various regulations on flame retardancy represented by the UL standards in the United States have been tightened, and many restrictions on use have been made. Has been receiving.

In general, as a flame retardant for a thermoplastic resin, a halogen-based flame retardant such as tetrabromobisphenol A, decabromodiphenyl oxide or hexabromobenzene is added and mixed, and an antimony compound is used in combination with a flame retardant auxiliary. It is used. However, such antimony compounds are suspected to be harmful and require careful handling. However, most of the antimony compounds are powdery, and there is a problem that dust is generated and scattered when kneaded with a thermoplastic resin. In addition, since it is powdery, it is difficult to classify and uniformly disperse it in a resin by dry blending or the like, which causes a problem that stable flame retardancy is hardly obtained.

[0004] In order to solve this problem, a master pellet in which antimony trioxide is kneaded in a high blend with a polypropylene resin or the like has been used. However, also in this case, since other resin components such as polypropylene are mixed in the thermoplastic resin to be used, there remains a problem that the original performance of the resin cannot be sufficiently exhibited.

In order to solve this problem, it is conceivable that an antimony compound is blended in the halogen-based flame retardant. However, even if the halogen-based flame retardant itself is in a powder form, it can be blended. Also, there is a problem that dust is scattered when kneading into the thermoplastic resin.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have obtained a general formula (Formula 1).

Embedded image (Where R ₁ and R ₃ represent a glycidyl group, a hydrogen group or

Embedded image Wherein R ₄ is a lower alkyl group, Y is a halogen atom, r and s are in the range of 0 to 5 and r + s is 5
The following integers, R ₂ is an alkylidene group having 1 to 4 carbon atoms, an alkylene group or a —SO ₂ — group, X is a halogen atom, p and q are in the range of 0 to 4, and all p and q are 0.
And n represents an integer of 20 or more in average degree of polymerization. ), The antimony compound is added to 100 parts by weight of the high molecular weight halogen-containing epoxy-modified product.
By kneading the flame retardant for antimony-containing thermoplastic resin containing 0 to 100 parts by weight into the thermoplastic resin,
It is found that there is no scattering to the surroundings due to dust during kneading, the antimony compound can be uniformly kneaded into the thermoplastic resin, good flame retardancy can be imparted, and the original physical properties of the thermoplastic resin are hardly impaired. This has led to the present invention.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The modified halogen-containing epoxy used in the present invention has the properties of a thermoplastic resin and can be easily molded. For this reason, even if the antimony compound is blended in a high content, there is little dispersion failure due to the formation of a masterbatch, and processing is easy. Furthermore, since this is a flame retardant for thermoplastic resins having excellent self-confidence and excellent heat resistance, it is a material that hardly adversely affects any thermoplastic resin, especially engineering plastics.

[0008] The proportion of the antimony compound in the high-molecular-weight halogen-containing epoxy-modified product can be increased when the molecular weight of the halogen-containing epoxy-modified product is high, and when the molecular weight is low, the antimony compound can be mixed. It becomes a brittle compound and powder is likely to be generated. For this reason, the molecular weight of the halogen-containing epoxy modified product must be a polymer type having an average degree of polymerization of 20 or more, and preferably 30 or more.

Regarding the compounding ratio of the antimony compound,
The larger the amount, the more bromine-based flame retardants can be used together, making it easier to use in various applications. However, 100 parts by weight of an antimony compound is mixed with 100 parts by weight of a halogen-containing epoxy-modified product. As a result, the composition becomes brittle, has physical properties in which powder is easily generated, and has poor dispersibility. Preferably a halogen-containing epoxy modified product 100
It is 70 parts by weight or less based on parts by weight. On the other hand, if the amount of the antimony compound is too small, sufficient flame retardancy cannot be obtained. Therefore, 10 parts by weight or more is required for 100 parts by weight of the halogen-containing epoxy modified product. Preferably, it is added in an amount of 25 parts by weight or more.

As an ideal production method for obtaining a halogen-containing epoxy-modified product used in the present invention, the present inventors have disclosed JP-A-1-185323 and JP-A-1-24052.
No. 0, the phenolic acid value is 1 (mgKOH / g) or less, and a catalyst with a very small remaining amount can be produced. A halogen-containing epoxy-modified product having extremely good thermal stability can be obtained.

That is, a halogenated bisphenol A and a halogenated bisphenol A diglycidyl ether, and optionally a halogenated phenol are also added, and a heating reaction is carried out in a solvent in the presence of a catalyst. A method in which the product is precipitated by pouring it into a large amount of a solvent that does not dissolve and then dried to obtain a halogen-containing epoxy-modified product, or halogenated bisphenol A and halogenated bisphenol A diglycidyl ether, optionally halogenated Phenol is also added, a catalyst is present, a heating reaction is performed in a solvent, and after the reaction is completed, the reaction solution is treated with an ion exchange resin. After removing the catalyst, the solvent is removed and dried to obtain a halogen-containing epoxy modified product. Is the way.

Examples of the antimony compound include antimony oxide, molybdenum oxide, tin oxide and the like. Preferably, antimony oxide compounds include antimony trioxide, antimony tetroxide, antimony pentoxide and sodium antimonate.

In addition, the compounding method of the antimony compound to the high-molecular-weight halogen-containing epoxy-modified product can be easily formed into a high-mixed pellet by using an ordinary extruder. In order to avoid the occurrence of dry blending, it is preferable to avoid dry blending and to provide a device that does not fly outside from a supply port or the like during the blending. More preferably, in order to improve the dispersibility of the antimony compound in the halogen-containing epoxy-modified product, it is preferable to mix the antimony compound with a twin-screw extruder.

In addition, there is no particular problem as long as the antimony compound can be uniformly dispersed in the high-molecular-weight halogen-containing epoxy-modified product using a high-viscosity stirrer. May be blended.

[0015] In the flame retardant composition of the present invention, other thermoplastic resins can be used in combination as long as the purpose thereof is not impaired. For example, polyester, polyamide, polycarbonate, polyurethane, polystyrene, AS, ABS, polyacetal, polyphenylene oxide, polyphenylene sulfide, polybutadiene, polyolefin, and the like can be blended in any ratio according to the purpose.

The flame retardant composition of the present invention may contain other known flame retardants (nitrogen compounds, phosphorus compounds, halogen compounds, etc.), and further various other additives, for example, UV absorbers, plasticizers, coloring agents, fillers, lubricants, stabilizers, and the like may be added.

Hereinafter, the present invention will be described specifically with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Synthesis Examples and Examples unless the gist is exceeded.

[0018]

Synthesis Example 1 790 g (1 mol) of brominated bisphenol A type epoxy resin (SR-TBA400, epoxy equivalent 395 (manufactured by Sakamoto Yakuhin Kogyo)) and 526 g (0.967 mol) of tetrabromobisphenol A (hereinafter abbreviated as TBA) And 600 g of dioxane were placed in a four-necked flask, 5 g of tetramethylammonium chloride was added, and the mixture was reacted at a reflux temperature (about 100 ° C.) under a nitrogen stream for 24 hours. After completion of the reaction, 2000 g of dioxane, cation exchange resin (Amberlyst 15 (manufactured by Organo)) 6
0 ml and 90 ml of an anion exchange resin (Diaion WA-20 (manufactured by Mitsubishi Kasei Kogyo)) were added, and the mixture was stirred at 50 to 60 ° C for 1 hour. After the solution was filtered to remove the ion exchange resin, the solvent in the filtrate was removed by a vacuum dryer to obtain a white powder product. This product has an acid value of 0.6 (mgKOH / g),
The epoxy equivalent was 18,000, the softening point was 240 ° C., the average degree of polymerization was n = 54, and the bromine content was 52.5% by weight.

[0019]

Synthesis Example 2 790 g (1 mol) of brominated bisphenol A type epoxy resin (SR-TBA400, epoxy equivalent 395 (manufactured by Sakamoto Yakuhin Kogyo)) and 492 g of TBA (0.1 mol) were used.
904 mol), 55.3 g (0.167 mol) of tribromophenol (hereinafter abbreviated as TBP) and 600 of dioxane.
g was placed in a four-necked flask, and after adding 5 g of tributylamine, the mixture was reacted at a reflux temperature (about 100 ° C.) for 24 hours under a nitrogen stream. After completion of the reaction, in the same manner as in Synthesis Example 1,
The product was obtained as a white powder. This product has an acid value of 0.6 (m
gKOH / g), epoxy equivalent 41,000, softening point 200
C., average degree of polymerization n = 21, and bromine content was 53.0% by weight.

[0020]

Synthesis Example 3 790 g (1 mol) of brominated bisphenol A type epoxy resin (SR-TBA400, epoxy equivalent 395 (manufactured by Sakamoto Yakuhin Kogyo)) and 475 g of TBA (0.1 mol)
873 mol) and 600 g of dioxane were placed in a four-necked flask, and after adding 5 g of tributylamine, the mixture was reacted at a reflux temperature (about 100 ° C.) for 24 hours under a nitrogen stream. After completion of the reaction, a white powder product was obtained in the same manner as in Synthesis Example 1. This product has an acid value of 0.4 (mg KOH / g), an epoxy equivalent of 4,900, a softening point of 190 ° C., an average degree of polymerization n = 15,
The bromine content was 52.2% by weight.

[0021]

Examples 1-3 and Comparative Examples 1-2 Antimony trioxide (PATOX-M manufactured by Nippon Seiko Co., Ltd.) was added to Synthesis Examples 1-3 at the ratio shown in Table 1 and kneaded with an extruder to form pellets. And flame retardants A to E were obtained. Table 1 shows the results.

Further, 100 g of the obtained flame retardants A to E were put into a 100-mesh sieve and shaken 100 times, and the amount of powdered products of 100 mesh or less was obtained. The results are shown in Table 1.

[0023]

[Table 1]

[0024]

Examples 4-6, Comparative Examples 3-4 PBT resin (Barox 310 (Nippon GE Plastics)), Synthesis Example 2
And the flame retardants A to C, antimony trioxide,
Glass fiber and the like were blended in the proportions shown in Table 2, pelletized by an extruder, and subjected to an Izod impact test and a UL-94 combustion test by an injection molding machine. The results are shown in Table 2.

[0025]

[Table 2]

Test Methods The Izod impact test was carried out according to JIS K7110 (with V notch, 1/8 "), and the flammability test was carried out according to UL-94 (1/16").

[0027]

As described above, the antimony-containing flame retardant obtained by blending an antimony compound with the high molecular weight type halogenated epoxy modified product of the general formula according to the present invention can maintain a thermoplastic shape, and can be used as a harmful powder. By using the resin as a thermoplastic resin with less scattering, a resin having stable flame retardancy and physical properties with less decrease in mechanical properties and the like can be obtained.

Continued on the front page F term (reference) 4H028 AA11 AA42 BA06 4J002 AA01X CF07X CH08W DE126 DE186 FD136

Claims (1)

[Claims] 1. A compound of the general formula (Wherein R ₁ and R ₃ are glycidyl groups, hydrogen groups or Wherein R ₄ is a lower alkyl group, Y is a halogen atom, r and s are in the range of 0 to 5 and r + s is 5
R ₂ represents an alkylidene group having 1 to 4 carbon atoms, an alkylene group or a —SO ₂ — group; X represents a halogen atom;
And n represents an integer of 20 or more in average degree of polymerization. ) With respect to 100 parts by weight of the high molecular weight halogen-containing epoxy modified product represented by
A flame retardant for an antimony-containing thermoplastic resin, which is blended with 100 to 100 parts by weight.