KR101136245B1 - High Anti-flammable Thermoplastic Resin Composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition excellent in flame retardancy, and more particularly, (A) 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer and 90 to 10% by weight of styrene-acrylonitrile copolymer. 100 parts by weight of resin; (B) 1 to 40 parts by weight of bromine organic flame retardant; And (C) 1 to 20 parts by weight of molybdenum trioxide; relates to a thermoplastic resin composition excellent in flame retardancy comprising a.

According to the present invention, there is an effect of providing a thermoplastic resin composition excellent in flame retardancy while maintaining excellent weather resistance, impact strength and fluidity.

Acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, bromine organic flame retardant, molybdenum trioxide, weather resistance, impact strength, flame retardancy

Description

High Anti-flammable Thermoplastic Resin Composition

The present invention relates to a thermoplastic resin composition excellent in flame retardancy, and more particularly, to a thermoplastic resin composition excellent in flame retardancy while maintaining excellent weather resistance, impact strength and fluidity.

Rubber modified styrene resins have excellent processability and physical properties, but have high flammability and should be given at least flame retardancy that satisfies the flame retardancy standard for electric and electronic products and office equipment.

As a method of imparting flame retardancy, a method of including a flame-retardant monomer and polymerizing the rubber-modified styrene-based resin and a method of mixing a flame-retardant and a flame-retardant aid into the manufactured rubber-modified styrene-based resin include halogen-based flame retardants. There are non-halogen flame retardants such as wine-based, nitrogen-based and hydroxide-based.

Since the non-halogen-based flame retardant is significantly lower in flame retardant efficiency than the halogen-based flame retardant, it should be added in an excessive amount, which inevitably degrades the mechanical properties of the rubber-modified styrene resin.

The halogen flame retardant has the effect of improving the flame retardancy while maintaining the mechanical properties of the rubber-modified styrene resin, double bromine flame retardant is particularly effective.

In the case of using the brominated flame retardant, by using a flame retardant aid such as a conventional antimony compound, it was possible to significantly reduce the amount of flame retardant required.

However, there is still a need for development of a rubber-modified styrene resin having excellent flame resistance while maintaining excellent weather resistance, impact strength and fluidity.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition excellent in flame resistance while maintaining excellent weather resistance, impact strength and fluidity.

These 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 (A) 100 parts by weight of a base resin consisting of 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer and 90 to 10% by weight of styrene-acrylonitrile copolymer; (B) 1 to 40 parts by weight of bromine organic flame retardant; And (C) 1 to 20 parts by weight of molybdenum trioxide; provides a thermoplastic resin composition excellent in flame retardancy comprising a.

According to the present invention, by introducing a bromine-based flame retardant and molybdenum trioxide together into an acrylonitrile-butadiene-styrene copolymer and a styrene-acrylonitrile copolymer, a thermoplastic resin composition having excellent flame resistance while maintaining excellent weather resistance, impact strength and fluidity can be obtained. It is effective to provide.

Hereinafter, the present invention will be described in detail.

The present inventors have confirmed that the thermoplastic resin composition prepared by mixing molybdenum trioxide with a bromine-based organic flame retardant and a flame retardant aid as a rubber-modified styrene resin as a flame retardant has excellent impact strength and flame retardancy, thereby completing the present invention.

The thermoplastic resin composition having excellent flame retardancy of the present invention includes (A) 100 parts by weight of a basic resin consisting of 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer and 90 to 10% by weight of styrene-acrylonitrile copolymer; (B) 1 to 40 parts by weight of bromine organic flame retardant; And (C) 1 to 20 parts by weight of molybdenum trioxide.

Although the acrylonitrile-butadiene-styrene copolymer is not particularly limited, butadiene rubber, acrylonitrile monomers and styrene monomers may be prepared in a powder state by emulsifying graft polymerization, then agglomeration, dehydration and drying. It is preferable that butadiene-based rubber having a particle diameter of 0.1 to 0.5 μm is included in 30 to 70 wt%.

The emulsion graft polymerization is based on 100 parts by weight of the total monomer content in the acrylonitrile-butadiene-styrene copolymer 30 to 70 parts by weight of butadiene rubber, 0.6 to 2 parts by weight of emulsifier, 0.2 to 1 parts by weight of molecular weight regulator and polymerization It is preferable to carry out continuously or collectively adding the monomer mixture which consists of 5-40 weight part of acrylonitrile and 20-65 weight part of styrene to the mixed solution which consists of 0.05-0.5 weight part of initiators.

The aggregation may be preferably carried out by 5% aqueous sulfuric acid solution.

The styrene-acrylonitrile copolymer has a weight average molecular weight of 50,000 to 150,000, preferably an acrylonitrile monomer content of 20 to 40% by weight, and may be used singly or in mixture of two or more kinds.

The bromine-based organic flame retardant is preferably included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin, the thermoplastic resin composition produced within this range does not significantly lower the mechanical strength and fluidity, excellent thermal stability and weather resistance It has the effect of having.

The bromine-based organic flame retardant is not particularly limited as long as it can be generally used in thermoplastic resins. Lomodiphenyl oxide, decabrodiphenylethane, brominated indane, ethylenebis (tetrabromophthalimide), tetrabromo bisphenol A, brominated epoxy oligomer, bis (tribromophenoxy) ethane, tris ( Tribromophenyl) cyanurate, tetrabromobisphenol A bis (allyl ether), derivatives thereof, and the like.

The molybdenum trioxide greatly improves the flame retardancy of the thermoplastic resin composition produced by synergistic effect when used together with the bromine-based organic flame retardant as a flame retardant aid.

The molybdenum-based compound is preferably included 1 to 20 parts by weight based on 100 parts by weight of the base resin, there is an effect of imparting sufficient flame retardancy, without lowering the impact strength within this range.

The thermoplastic resin composition may further include one or more additives selected from the group consisting of impact modifiers, lubricants, heat stabilizers, anti-drip agents, antioxidants, light stabilizers, sunscreens, pigments and inorganic fillers.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One

38 parts by weight of an ABS copolymer DP270 grade manufactured by LG Chem by emulsion graft polymerization using butadiene rubber latex having an average particle diameter of 0.3 μm, and a styrene-acrylonitrile containing 25% by weight of acrylonitrile and a weight average molecular weight of 120,000. Tetrabromobisphenol A, a bromine-based organic flame retardant, in 100 parts by weight of a basic resin composed of 42 parts by weight of a nitrile copolymer and 20 parts by weight of a styrene-acrylonitrile copolymer having an acrylonitrile content of 23% by weight and a weight average molecular weight of 110,000. 25 parts by weight, 5 parts by weight of molybdenum trioxide, a flame retardant aid, 0.5 parts by weight of antioxidant, 1 part by weight of lubricant, and 0.75 parts by weight of anti-dripping agent were added and mixed uniformly using a Henschel mixer, and then pelletized through a twin screw extruder. A thermoplastic resin composition was prepared.

The pellet-type thermoplastic resin composition was injection molded to prepare specimens 1/8, 1/10, 1/12 and 1/16 inch thick for flame retardancy testing.

Comparative Example 1

Except for the use of zinc borate instead of molybdenum trioxide as a flame retardant in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 2

Except for using aluminum hydrate instead of molybdenum trioxide as a flame retardant in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 3

Except for using the manganese sulfate instead of molybdenum trioxide as a flame retardant in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 4

The same method as in Example 1 was carried out except that molybdenum trioxide as a flame retardant aid was not used in Example 1.

Example 2

Except for using the bromine-based organic flame retardant tetrabromobisphenol A in 30 parts by weight was carried out in the same manner as in Example 1.

Comparative Example 5

Except for the use of zinc borate instead of molybdenum trioxide as a flame retardant in Example 2 was carried out in the same manner as in Example 2.

Comparative Example 6

Except for using a zinc oxide instead of molybdenum trioxide as a flame retardant in Example 2 was carried out in the same manner as in Example 2.

Comparative Example 7

Example 2 was carried out in the same manner as in Example 2, except that magnesium chloride was used instead of molybdenum trioxide as a flame retardant aid.

Comparative Example 8

Except for not using molybdenum trioxide as a flame retardant aid in Example 2 was carried out in the same manner as in Example 2.

[Test Example]

Flame retardancy of the thermoplastic resin composition specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 8 was measured by the following method, and the results are shown in Tables 1 and 2 below.

* Flame retardancy: Based on the UL-94 test standard, it was measured for specimens 1/8, 1/10, 1/12, 1/16 inch thick. The first burn and the second burn were each marked V-0 when the burned-out time was less than 10 seconds after burning on the flame for 10 seconds, respectively. Marked as -2. If the burning time of each specimen exceeds 30 seconds or if the sum of the burning and glowing times of five specimens exceeds 250 seconds, burning is indicated.

division Example Comparative example I
year
castle Psalm Thickness
(inch) One One 2 3 4 1/8 V-2 burning burning burning burning 1/10 V-2 burning burning burning burning 1/12 V-2 burning burning burning burning 1/16 burning burning burning burning burning

As shown in Table 1, the thermoplastic resin composition (Example 1) comprising tetrabromobisphenol A as a flame retardant and molybdenum trioxide as a flame retardant according to the present invention has a flame retardancy of V-2, but includes a flame retardant. If not included (Comparative Example 4), in the case of containing zinc borate (Comparative Example 1), aluminum hydrate (Comparative Example 2) or manganese sulfate (Comparative Example 3) instead of molybdenum trioxide as a flame retardant, it does not exhibit UL flame retardancy standards Could not confirm.

division Example Comparative example I
year
castle Psalm Thickness
(inch) 2 5 6 7 8 1/8 V-0 V-2 V-2 burning V-0 1/10 V-0 burning burning burning burning 1/12 V-0 burning burning burning burning 1/16 V-2 burning burning burning burning

As shown in Table 2, the thermoplastic resin composition (Example 2) further comprises a small amount of tetrabromobisphenol A bromine-based organic flame-retardant compared to the thermoplastic resin composition of Example 1 according to the present invention (Example 2) It showed a flame retardancy of VO in the 1/8 to 1/12 inch thick specimens, and V-2 in the 1/16 inch thick specimens.

However, a thermoplastic resin composition (Comparative Examples 5 to 7) each containing zinc borate, aluminum hydrate, and manganese sulfate instead of molybdenum trioxide as a flame retardant aid (Comparative Examples 5 to 7) added a small amount of tetrabromobisphenol A to Example 1 which is a brominated organic flame retardant. Despite this, there was no significant change in flame retardancy, and the effect was insignificant compared to the case where no flame retardant aid was included (Comparative Example 8).

Therefore, the thermoplastic resin compositions (Examples 1 and 2) of the present invention was confirmed that the flame retardancy is greatly improved by the synergistic effect of the combination of the bromine-based organic flame retardant and molybdenum trioxide.

Claims (5)

(A) 100 parts by weight of a base resin consisting of 10 to 90% by weight of acrylonitrile-butadiene-styrene copolymer and 90 to 10% by weight of styrene-acrylonitrile copolymer; (B) 1 to 40 parts by weight of bromine organic flame retardant; And (C) 1 to 20 parts by weight of molybdenum trioxide; The acrylonitrile monomer content included in the styrene-acrylonitrile copolymer in the base resin (A) is in the range of 20 to 40% by weight. Thermoplastic resin composition excellent in flame retardancy. The method of claim 1, The acrylonitrile-butadiene-styrene copolymer is prepared by emulsion graft polymerization of butadiene rubber, acrylonitrile monomer and styrene monomer, and the content of butadiene rubber is 30 to 70% by weight Thermoplastic resin composition excellent in flame retardancy. The method of claim 1, The acrylonitrile-butadiene-styrene copolymer is composed of 30 to 70% by weight of butadiene rubber, 5 to 40% by weight of acrylonitrile monomer and 20 to 65% by weight of styrene monomer. Thermoplastic resin composition excellent in flame retardancy The method of claim 1, The styrene-acrylonitrile copolymer is a single or two or more styrene-acrylonitrile copolymers having a weight average molecular weight of 50,000 to 150,000 Thermoplastic resin composition excellent in flame retardancy. 5. The method according to any one of claims 1 to 4, The thermoplastic resin composition further comprises at least one additive selected from the group consisting of impact modifiers, lubricants, heat stabilizers, anti-drip agents, antioxidants, light stabilizers, sunscreens, pigments and inorganic fillers. Thermoplastic resin composition excellent in flame retardancy.