JPH02228356A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To prepare a flame-retardant resin compsn. which gives a molding with an excellent heat resistance and impact strength without showing bleeding by compounding an org. polymer with a brominated polyester comprising dibromoneopentyl glycol and a dicarboxylic acid. CONSTITUTION:An org. polymer (e.g. polypropylene) is compounded with a brominated polyester comprising dibromoneopentyl glycol and at least one dicarboxylic acid selected from the group consisting of oxalic, malonic, maleic, succinic, fumaric, glutaric, adipic, itaconic, methylsuccinic, dichloromaleic, dibromonaleic, dichlorosuccinic, dibromosuccinic, benzenedicarboxylic, toluenedicarboxylic, cyclohexanedicarboxylic, naphthalenedicarboxylic, tetrachloronaphthalenedicarboxylic, tetrabromonaphthalenedicarboxylic, tetrachlorophthalic, tetrabromophthalic, 3,6-endomethylenetetrahydrophthalic, dibromoterephthalic, and chlorendic acids, and anhydrides thereof.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a flame-retardant resin composition, particularly a composition that does not cause bleeding and can form a molded article with excellent heat resistance and impact resistance. Regarding.

(Prior art) Thermoplastic resins such as polypropylene, polystyrene, and ABS are available at relatively low prices and have excellent properties such as being easy to mold, so they are used in all kinds of household goods, including electronic parts and automobile parts. Widely used. However, these resins are easily flammable, and once a fire occurs, they will easily burn and disappear. Cable fires have a particularly serious impact on society. For this reason, some of the fields in which these resins are used, such as electrical products and automobile interior parts, are now required by law to be flame retardant. For example, the MVSS-302 flame retardant regulations for automobiles in the United States, the UL standards (Underwriter's Lab
oratories Inc.), etc. are known.

As a method of imparting flame retardancy to thermoplastic resin.

A method of adding a flame retardant to the resin may be mentioned. Flame retardants include inorganic compounds, organic phosphorus compounds, organic halogen compounds, etc. Among them, organic halogen compounds, especially organic bromine compounds, exhibit excellent flame retardant effects. Commonly used organic bromine compounds include decabromobiphenyl oxide, octabromobiphenyl oxide, tetrabromobisphenol A, hexabromobenzene, hexabromocyclododecane, and the like. However, since these are single compounds with small molecular weights, they have poor compatibility with resins. In particular, when a molded article is prepared by blending it with a polyolefin resin, the molded article.

Bleeding, where the flame retardant gradually rises to the surface over time, can be seen. Blending single compounds also causes a decrease in the mechanical properties of the molded product.

Two methods are known to prevent bleeding. One of these is the use of so-called reactive flame retardants. This reactive flame retardant.

It is a polymerizable monomer containing a flame-retardant element, and during polymerization, this monomer reacts and is incorporated into the resin skeleton, thereby producing a flame-retardant resin. Examples of reactive flame retardants include tribromophenyl acrylate and tribromophenyl methacrylate.

Examples include tribromophenoxyethyl acrylate, tribromophenoxyethyl methacrylate, and bromostyrene. However, these reactive flame retardants are generally expensive because they are not easy to manufacture. Moreover, it is not simply mixed into a thermoplastic resin, but is used as a raw material during the production of the resin.

It is complicated because it requires preparing flame-retardant resin.

This method is not commonly used at present.

Another method to prevent bleed is to use polymeric or oligomeric flame retardants and mix them with the resin. This method is common today. Examples of polymeric or oligomeric flame retardants include brominated polycarbonate-based brominated epoxy resins and brominated polystyrene.

Heptabromobenzyl polyacrylate and the like have already been reported. However, in all of these bromine compounds, bromine is substituted on the benzene ring, so bromine cannot be eliminated unless high heat is applied. In other words, flame retardancy is weak. Therefore, in order to impart sufficient flame retardancy, it is necessary to add a large amount to the resin. As a result, the mechanical properties such as impact resistance of the obtained molded article are significantly reduced.

(Problem to be solved by the invention) The present invention solves the above-mentioned conventional drawbacks.

The objective is to provide a flame-retardant resin composition that can form a flame-retardant molded article without degrading mechanical properties such as impact resistance and without causing bleeding.

(Means for Solving the Problems) The flame-retardant resin composition of the present invention comprises dibromoneopentyl glycol (2,2-bis(dibromomethyl)-1,3-
propanediol] and dicarboxylic acid as constituent components, and an organic polymer, thereby achieving the above object.

The dicarboxylic acids that are constituents of the bromine-containing polyester contained in the flame-retardant resin composition of the present invention include oxalic acid, malonic acid, maleic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, itaconic acid, methylsuccinic acid,
Dichloromaleic acid.

Dibromomaleic acid, dichlorosuccinic acid, dibromosuccinic acid, benzene dicarboxylic acid, toluene dicarboxylic acid,
Tetrachlorophthalic acid, tetrabromophthalic acid, dibromoterephthalic acid, cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, het acid, 3,6-endomethylenetetrahydrophthalic acid, tetrachloronaphthalene dicarboxylic acid, tetrabromonaphthalene dicarboxylic acid, and/or .

Examples include acid anhydrides of these.

The bromine-containing polyester used in the present invention is:

It can be prepared by conventional polyester synthesis methods.

For example, it can be easily synthesized by a dehydration reaction between an acid and an alcohol. In this method.

The dicarboxylic acid or its acid anhydride and dibromoneopentyl glycol are heated in an organic solvent (e.g. toluene) in the presence of an acid catalyst (e.g. para-toluenesulfonic acid di-sulfuric acid, etc.) and reacted under reflux of toluene. ) and remove by-product water. The molecular weight of the resulting polyester can be adjusted as appropriate by changing the molar ratio of dicarboxylic acid or its acid anhydride and dibromoneopentyl glycol. An alternative method for preparing bromine-containing polyesters includes transesterification. In this method, a bromine-containing polyester is synthesized by a dealcoholization reaction between an ester of the dicarboxylic acid and dibromoneopentyl glycol. As the ester of the dicarboxylic acid, alkyl esters such as methyl ester, propyl ester, butyl ester, etc. are used.

The reaction proceeds by heating in the presence of an alkaline catalyst such as sodium methylate to remove by-product alcohol.

As the organic polymer contained in the flame retardant resin composition of the present invention, both synthetic polymer compounds and natural polymer compounds can be used. Synthetic polymer compounds include vinyl monomer homopolymers or copolymers, unsaturated polyester resins, polyurethane resins, polyamide resins, polyester polymers, polyvinyl alcohol resins, polycarbonate resins, 1 polyether type Examples include resins, phenolic resins, epoxy resins, polyphenylene oxide polymers, and polyimide resins. The above vinyl monomers include ethylene, propylene, butylene, phthalene,
Isoprene, chlorobrene.

Examples include vinyl chloride, styrene, α-methylstyrene, vinyl acetate, acrylic ester, methacrylic ester, and acrylonitrile. Examples of natural polymer compounds include wood, cotton, regenerated cellulose, and wool.

The bromine-containing polyester thus obtained can be used as an additive flame retardant or.

In some compounds, it is used as a reactive flame retardant.

The bromine-containing polyester used as a reactive flame retardant is maleic and pentafumaric acid in which the dicarboxylic acid constituting the polyester has an unsaturated group.

These compounds are itaconic acid, dichloromaleic acid, and dibromomaleic acid. Such bromine-containing polyesters can be used, for example, in flame-retardant unsaturated polyester resins.

In the composition of the present invention, the amount of the bromine-containing polyester is usually 2 to 100 parts by weight based on 100 parts by weight of the organic polymer.
It is contained in a proportion of 5 to 30 parts by weight, preferably 5 to 30 parts by weight. If the amount is less than this range, no flame retardant effect can be obtained. If the amount exceeds this range, there is no problem, but the retardancy and flame resistance of the resulting resin will not improve beyond a certain level. A flame retardant aid such as antimony trioxide, an antioxidant, and a filler may be added to the composition within a range that does not affect the physical properties of the resulting flame retardant resin.

The above organic polymer and bromine-containing polyester.

The mixture may be mixed by various known methods. For example, a bromine-containing polyester is added during a polymerization reaction to obtain an organic polymer, or when molding an organic polymer into a desired shape. Alternatively, a method may be adopted in which a molded article or a woven or nonwoven fabric made of an aggregate of fibers is treated with a solution or dispersion containing a bromine-containing polyester. There is also a method of using it as a master batch containing bromine-containing polyester and resin.

Since the bromine atom of dibromoneopentyl glycol used in the above-mentioned bromine-containing polyester is bonded to an aliphatic carbon, the resulting bromine-containing polyester has a flame retardant effect compared to a bromine compound in which hydrogen in the benzene ring is replaced with a bromine atom. expensive. Therefore, high flame retardancy can be imparted by adding a small amount. Since this bromine-containing polyester is a relatively long-chain polymer, it has good compatibility with organic polymers and does not cause bleeding. Furthermore, even when used as an additive flame retardant, bromine-containing polyester containing dicarboxylic acid with unsaturated bonds has characteristics such as graft polymerization with the resin during molding, making it difficult to cause bleeding. There is.

The above-mentioned bromine-containing polyester is a relatively flexible long-chain polymer having ester bonds, and is not contained in large amounts.1 The molded article using the composition of the present invention has excellent mechanical properties, especially impact resistance. .

(Example) The present invention will be described below with reference to an example. Parts as used herein refer to parts by weight.

<Example 1> (A) Preparation of oxalic acid/dibromoneopentyl glycol polyester 126 g (1 mol) of oxalic acid/dihydrate was placed in a reactor equipped with a stirrer, a thermometer, and a water separation reflux condenser tube.

262 g (1 mol) of dibromoneopentyl glycol.

Para-toluenesulfonic acid 0.5g and toluene 300g
was added and mixed. This was heated to about 100°C and reacted for about 6 hours while refluxing toluene, and the water of crystallization of oxalic acid and the water by-produced in the reaction were removed from the reactor. It was filtered off at room temperature and washed with methanol. After drying.

310 g of white powder product were obtained. The bromine content of the product was 50.2% by weight.

(B) Evaluation of flame-retardant molded article To 100 parts of polypropylene, 15 parts of oxalic acid/dibromoneopentyl glycol polyester obtained in section (^) as a flame retardant, and 7.5 parts of antimony trioxide.
parts were blended and kneaded. The kneaded material was put into an injection molding machine and molded to obtain a test piece. Using this test piece, flame retardancy, bleedability, and impact strength were measured as follows.

The flame retardancy of the test piece was determined by the dish UL-94 test method. The flame retardance of the test piece is V-0, V-1, V-2° and H
It was classified into four types: B.

Punishability test piece (used in the υL-94 test method) was 120
After 24 hours at °C, leaching of flame retardant from the specimens was determined visually.

Izo impact strength of the notched test piece was measured according to the test method of ASTM D-256.

These results are shown in Table 1, and are shown in Examples 2.4 and 5. The results of Comparative Examples 1 to 4 are also shown in Table 1.

<Example 2> (A) Maleic acid/dibromoneopentyl glycol/
Preparation of polyester The procedure was repeated in the same manner as in Example 1, except that 98 g (1 mol) of maleic anhydride was used instead of 126 g (1 mol) of oxalic acid dihydrate, and 335 g of a high viscosity liquid was obtained. . The bromine content of the obtained product was 46.51% by weight.

(B) Evaluation of flame-retardant molded article Bromine-containing polyester 17 obtained in this example (^)
Evaluation was carried out according to Example 1 (B) using a sample.

<Example 3> Preparation of succinic acid/dibromoneopentyl glycol polyester Same as Example 1 except that 118 g (1 mol) of succinic acid was used instead of 126 g (1 mol) of oxalic acid dihydrate. 337 g of high viscosity liquid was obtained. The bromine content of the obtained product was 46.4i [4%].

<Example 4> The same as Example 1 except that the amount of oxalic acid/dibromoneopentyl glycol polyester was 30 parts and antimony dioxide was not used.

<Example 5> The same as Example 2 except that the amount of maleic acid/dibromoneopentyl glycol polyester was 35 parts and antimony dioxide was not used.

<Comparative Example 1> (A) Preparation of oxalic acid/4.4'' bis(2-hydroxyethyl)tetrabromobisphenol A polyester 4.4'bis(2- The same procedure as in Example 1 was carried out except that 632 g (1 mol) of hydroxyethyl)tetrabromobisphenol A was used to obtain 680 g of powder.The bromine content of the obtained product was 46.7% by weight.
Met.

(B,) Evaluation of flame-retardant molded article Bromine-containing polyester 20 obtained in section (A) of this comparative example
Evaluation was carried out according to Example 1 (B) using a sample.

Comparative Example 2> Decabromo biphenyl oxide 20 commercially available as a flame retardant
The procedure is the same as in Example 1 (B) except that 1 part is added.

Comparative Example 3 This was the same as in Example 1 (B) except that 20 parts of commercially available brominated polystyrene was added as a flame retardant.

Comparative Example 4 The same as Comparative Example 1 except that the amount of oxalic acid/4,4'bis(2-hydroxyethyl)tetrabromobisphenol A polyester was 40 parts and antimony trioxide was not used.

(The following is a blank space) <Example 6> 15 parts of the oxalic acid/dibromoneopentyl glycol polyester obtained in Example 1 (A) and 5 parts of antimony dioxide were blended and kneaded with 100 parts of ABS resin.

Put the kneaded mixture into an injection molding machine and mold it.

A test piece was obtained. Using this test piece, flame retardancy, bleedability, and impact strength were measured in the same manner as in Example 1 (B). These results are shown in Table 2. The results of Example 7 and Comparative Examples 5 and 6, which will be described later, are also shown in Table 2.

<Example 7> The same as Example 6 except that 17 parts of the succinic acid/dibromoneopentyl glycol polyester obtained in Example 3 was blended instead of 15 parts of the oxalic acid/dibromoneopentyl glycol polyester.

Comparative Example 5 The same as Example 6 except that 20 parts of commercially available tetrabromobisphenol A was added instead of 15 parts of oxalic acid/dibromoneopentyl glycol polyester.

Comparative Example 6 The same as Example 6 except that 20 parts of commercially available pentabromobenzyl polyacrylate was blended instead of 15 parts of oxalic acid/dibromoneopentyl glycol polyester.

(The following is a blank space) <Example 8> 15 parts of the oxalic acid/dibromoneopentyl glycol polyester obtained in Example 1 (A) and 5 parts of antimony dioxide were blended and kneaded with 100 parts of PBT resin.

Put the kneaded mixture into an injection molding machine and mold it.

A test piece was obtained. Using this test piece, flame retardancy, bleedability, and impact strength were measured in the same manner as in Example 1(B). These results are shown in Table 3.

<Example 9> Same as the example day except that 17 parts of maleic acid/dibromoneopentyl glycol polyester obtained in Example 2 (A) was blended instead of 15 parts of oxalic acid/dibromoneopentyl glycol polyester. be.

<Example 10> The same as Example 8 except that the amount of oxalic acid/dibromoneopentyl glycol polyester was 30 parts and antimony trioxide was not used.

<Example 11> The same as Example 9 except that the amount of maleic acid/dibromoneopentyl glycol polyester was 35 parts and antimony trioxide was not used.

Comparative Example 7 Commercially available brominated polycarbonate 2 was used instead of 15 parts of oxalic acid/dibromoneopentyl glycol polyester.
The procedure is the same as in Example 8 except that 0 part was added.

Comparative example day> The same as Example 8 except that 20 parts of commercially available brominated polystyrene was blended instead of 15 parts of oxalic acid/dibromoneopentyl glycol polyester.

<Comparative Example 9> The same as Comparative Example 8 except that the amount of brominated polystyrene was 40 parts and antimony trioxide was not used.

(Left below) (Effects of the Invention) According to the present invention, a flame-retardant resin composition that does not cause bleeding and can form a molded article with excellent impact strength can be obtained. The compositions are suitable for various products requiring flame retardancy, e.g.

It can be widely used in automobile parts, interior parts, electronic parts, household appliances such as curtains, beds, etc.

that's all

Claims (1)

[Claims] 1. A flame-retardant resin composition containing a bromine-containing polyester containing dipromoneopentyl glycol and dicarboxylic acid as constituent components, and an organic polymer. 2. The dicarboxylic acid is oxalic acid, malonic acid, maleic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, itaconic acid, methylsuccinic acid, dichloromaleic acid,
Dibromomaleic acid, dichlorosuccinic acid, dibromosuccinic acid, benzene dicarboxylic acid, toluene dicarboxylic acid,
Tetrachlorophthalic acid, tetrabromophthalic acid, dibromoterephthalic acid, cyclohexanedicarboxylic acid, naphthalene dicarboxylic acid, het acid, 3,6-endomethylenetetrahydrophthalic acid, tetrachloronaphthalene dicarboxylic acid, tetrabromonaphthalene dicarboxylic acid and these acids The flame-retardant resin composition according to claim 1, which is at least one selected from the group consisting of anhydrides.