KR100969454B1 - Thermoplastic flame retardant resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic flame-retardant resin composition, 1 to 10% by weight of the phosphite compound based on 100 parts by weight of the base resin consisting of 10 to 80% by weight of the rubber-modified styrene-containing graft copolymer and 20 to 90% by weight of the styrene-containing copolymer The present invention relates to a thermoplastic flame-retardant resin composition comprising a portion, and has an effect of providing a thermoplastic flame-retardant resin composition having excellent flame retardancy and excellent impact strength and heat resistance.

Thermoplastic flame retardant resin composition, rubber modified styrene-containing graft copolymer, styrene-containing copolymer, phosphite compound, flame retardancy, impact strength, heat resistance

Description

Thermoplastic flame retardant composition {THERMOPLASTIC FLAME RETARDANT RESIN COMPOSITION}

The present invention relates to a thermoplastic flame retardant resin composition, and more particularly, to a thermoplastic flame retardant resin composition having excellent flame retardancy and excellent impact strength and heat resistance.

Rubber modified styrene resins have excellent processability and excellent physical and cosmetic properties such as impact strength, and are widely used in electrical and electronic products and office equipment. Such electrical and electronic products and office equipment have a risk of fire, and studies to impart flame retardance to rubber-modified styrene resins have been continuously conducted.

As a method of imparting flame retardancy to rubber-modified styrene resins, it is known that a halogen compound is used as a flame retardant. However, since halogen-based compounds generate gases that corrode molds during molding of resins, and emit toxic gases that are harmful to humans during combustion, they are subject to restrictions due to tightening environmental regulations.

Accordingly, much attention is focused on providing flame retardancy to rubber-modified styrene resins without using halogen compounds as flame retardants, and rubber-modified styrene flame-retardant resin compositions prepared by using phosphate ester compounds as flame retardants include copiers, It is widely used for office equipment such as printing.

However, since the phosphate ester compound used as a flame retardant has a low melting point and is easily decomposed at the processing temperature of the resin, a resin composition using the same may cause pyrolysis gas and mold deposit phenomenon during long processing, resulting in poor appearance of the product. There is this.

In order to overcome this problem, Japanese Patent Application Laid-Open No. 5-1079 discloses a flame retardant having a diphosphate ester structure having an aromatic phenyl group as a linkage to improve the volatility problem of the phosphate ester compound. 043769 discloses a flame retardant having a structure in which a substituent having 12 to 25 carbon atoms is introduced into a phenyl group. However, the above conventional technologies have a problem in that heat resistance and mechanical properties are degraded.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic flame-retardant resin composition excellent in flame retardancy and excellent impact strength and heat resistance.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is 10 to 80% by weight of the rubber-modified styrene-containing graft copolymer and 20 to 90% by weight of the styrene-containing copolymer based on 100 parts by weight of the phosphite compound 1 to 10% by weight It provides a thermoplastic flame-retardant resin composition comprising a part.

Hereinafter, the present invention will be described in detail.

The base resin of the present invention is composed of 10 to 80% by weight of rubber-modified styrene-containing graft copolymer and 20 to 90% by weight of styrene-containing copolymer.

The rubber-modified styrene-containing graft copolymer is prepared by graft copolymerization of 10 to 60 wt% of the rubber component with 30 to 65 wt% of the styrene compound and 10 to 30 wt% of the acrylic compound.

As the rubber component, a polybutadiene, a styrene-butadiene copolymer, a polyisoprene or a butadiene-isoprene copolymer, or the like may be used alone or in combination of two or more thereof.

As the styrene compound, styrene, alphamethyl styrene, nuclear substituted styrene, or the like may be used alone or in combination of two or more thereof.

As said acryl-type compound, acrylonitrile, methyl methacrylate, butyl acrylate, etc. can be used individually or in mixture of 2 or more types.

The rubber-modified styrene-containing graft copolymer is preferably an acrylonitrile-butadiene-styrene graft copolymer (acrylonitrile-butadiene-styrene, ABS) in which acrylonitrile and styrene are graft copolymerized with butadiene rubber.

The rubber-modified styrene-containing graft copolymer is preferably included in 10 to 80% by weight 100 parts by weight of the base resin. When included in the content is excellent mechanical strength, such as impact resistance.

The styrene-containing copolymer is prepared by copolymerizing 50 to 80% by weight of the styrene compound and 20 to 50% by weight of the acrylic compound.

As the styrene-based compound, styrene, alphamethyl styrene, or nuclear substituted styrene may be used alone or in mixture of two or more. The acryl-based compound may be acrylonitrile, methyl methacrylate, or butyl acrylate alone or two. It can mix and use species.

The styrene-containing copolymer is preferably included in 20 to 90% by weight 100 parts by weight of the base resin. When included in the content is excellent mechanical strength and dimensional stability, such as impact resistance.

The rubber-modified styrene-containing graft copolymer and the styrene-containing copolymer may be prepared by a conventional polymerization method, and preferably prepared by bulk polymerization or emulsion polymerization.

The phosphite compound of the present invention is a flame retardant for imparting flame retardancy to a base resin.

Examples of the phosphite compound include trialkyl phosphites such as trimethyl phosphite, triethyl phosphite, and triisodecyl phosphite; Trialkyl-aryl phosphites such as trisnonylphenyl phosphite, isodecyldiphenyl phosphite and diisodecylphenyl phosphite; Alternatively, two or more kinds of triaryl phosphites having the structure of Formula 1 may be mixed and used alone, preferably triaryl phosphite is used, and more preferably triaryl phosphite substituted with an alkyl group is used. It is.

In Formula 1, Ar ₁ to Ar ₃ is an aryl group substituted with 1 to 3 phenyl group or alkyl group having 1 to 18 carbon atoms.

The phosphite compound is preferably included in 1 to 10 parts by weight based on 100 parts by weight of the base resin. When included in the content, while maintaining the flame retardancy, it is excellent in impact resistance.

The thermoplastic flame-retardant resin composition comprising the above components may further include one or more additives selected from lubricants, heat stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers, depending on the application.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example 1

<Basic resin manufacturing>

As the rubber-modified styrene-containing graft copolymer, an acrylonitrile-butadiene-styrene graft copolymer prepared by graft copolymerization of 50% by weight of butadiene rubber, 14% by weight of acrylonitrile and 36% by weight of styrene by emulsion polymerization was used. .

As the styrene-containing copolymer, a styrene-acrylonitrile copolymer prepared by copolymerizing 73% by weight of styrene and 27% by weight of acrylonitrile by emulsion polymerization was used.

<Preparation of thermoplastic flame retardant resin composition>

Tris represented by the following formula (2,4-) as a phosphite compound in 100 parts by weight of the base resin including 23 parts by weight of the acrylonitrile-butadiene-styrene graft copolymer and 77 parts by weight of the styrene-acrylonitrile copolymer. 4 parts by weight of di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals) was added thereto, mixed in a Henschel mixer, and extruded at a temperature range of 180 to 220 ° C. in a twin screw extruder to prepare pellets.

Example  2

The same method as in Example 1 except that 8 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals), a phosphite compound, was used as a flame retardant in Example 1. It was.

Comparative example  One

Except that the phosphite compound which is a flame retardant in Example 1 was not used, it was carried out in the same manner as in Example 1.

Comparative example  2

In Example 1, 8 parts by weight of triphenyl phosphate (manufactured by Nippon Shopal Chemical Co., Ltd.), which is a phosphate compound, was used in place of the phosphite compound as a flame retardant.

Comparative example  3

The same method as in Example 1 except that 12 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals), a phosphite compound, was used as a flame retardant in Example 1. It was.

[Test Example]

The thermoplastic flame-retardant resin composition pellets prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were injection molded to prepare a specimen, and the physical properties were measured by the following method, and the results are shown in Table 1 below.

* Impact Strength (kg · cm / cm) —Measured against 1/8 ”thick specimens in accordance with ASTM D256.

* Heat resistance (℃)-The heat deflection temperature was measured on a 1/4 ”thick specimen in accordance with ASTM D648.

* Flame retardancy-Measured on 1/8 ”thick specimens in accordance with UL94 VB flame retardant specification.

division Example Comparative example One 2 One 2 3 Suzy
Ingredient
(Parts by weight) Rubber modified styrene-containing graft copolymer 23 23 23 32 23 Styrene-containing
Copolymer 77 77 77 77 77 Phosphite
compound 4 8 - - 12 Phosphate Ester Compound - - - 8 - Impact strength (kgcm / cm) 33 38 32 18 9 Heat deflection temperature (℃) 83 85 84 68 85 Flame retardancy V-2 V-2 NR V-2 V-2  * NR- No Rating

Through Table 1, the thermoplastic flame-retardant resin composition of Examples 1 to 2 containing 1 to 10 parts by weight of the phosphite compound as a flame retardant in the base resin according to the present invention was confirmed that the impact strength, heat resistance and flame retardancy excellent.

On the other hand, Comparative Example 1, which does not include a phosphite compound, has significantly reduced flame retardancy, while Comparative Example 2, which includes a phosphate ester-based compound as a flame retardant, has a flame retardancy equivalent to that of Examples, but has reduced impact strength and heat resistance. In addition, Comparative Example 3 containing an excess of the phosphite compound was confirmed that the impact strength is significantly reduced.

As described above, according to the present invention, there is an effect of providing a thermoplastic flame-retardant resin composition having excellent flame resistance and excellent impact strength and heat resistance.

Claims (9)

It comprises 1 to 10 parts by weight of a phosphite compound based on 100 parts by weight of the base resin consisting of 10 to 80% by weight of the rubber-modified styrene-containing graft copolymer and 20 to 90% by weight of the styrene-containing copolymer, The phosphite compound is characterized in that the triaryl phosphite compound having the formula Thermoplastic Flame Retardant Composition [Formula 1]

(In Formula 1, Ar ₁ to Ar ₃ represents a phenyl group or an aryl group having 1 to 3 substituted alkyl groups having 1 to 18 carbon atoms.) The method of claim 1, The rubber-modified styrene-containing graft copolymer is characterized in that the graft copolymer 30 to 65% by weight of the styrene compound and 10 to 30% by weight of the acrylic compound in 10 to 60% by weight of the rubber component Thermoplastic flame retardant resin composition. 3. The method of claim 2, The rubber component is at least one selected from the group consisting of polybutadiene, styrene-butadiene copolymer, polyisoprene and butadiene-isoprene copolymer, The styrene-based compound is at least one selected from the group consisting of styrene, alphamethyl styrene, and nuclear substituted styrene, The acrylic compound is at least one selected from the group consisting of acrylonitrile, methyl methacrylate, and butyl acrylate Thermoplastic flame retardant resin composition. The method of claim 1, The styrene-containing copolymer is characterized in that 50 to 80% by weight of the styrene compound and 20 to 50% by weight of the acrylic compound is copolymerized Thermoplastic flame retardant resin composition. The method of claim 4, wherein The styrene-based compound is at least one selected from the group consisting of styrene, alphamethyl styrene, and nuclear substituted styrene, The acrylic compound is at least one selected from the group consisting of acrylonitrile, methyl methacrylate and butyl acrylate Thermoplastic flame retardant resin composition. The method of claim 1, The phosphite compound is characterized by further using a trialkyl phosphite compound or a trialkyl aryl phosphite compound Thermoplastic flame retardant resin composition. The method of claim 6, The trialkyl phosphite compound is selected from the group consisting of trimethyl phosphite, triethyl phosphite, and triisodecyl phosphite, The trialkylaryl phosphite compound is selected from the group consisting of trisnonylphenyl phosphite, isodecyldiphenyl phosphite, and diisodecylphenyl phosphite, characterized in that Thermoplastic flame retardant resin composition. The method of claim 1, The thermoplastic flame-retardant resin composition further comprises at least one additive selected from lubricants, heat stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments, and inorganic fillers. Thermoplastic flame retardant resin composition. The method of claim 1, The phosphite compound is characterized by using tris (2,4-di-t-butylphenyl) phosphite of formula (2) Thermoplastic Flame Retardant Composition [Formula 2]