KR100241115B1 - A retard resin composition with excellant compactability - Google Patents

Abstract

The thermoplastic resin composition of the present invention (A) (a ₁ ) 35 to 65% by weight of the rubbery polymer 30 to 50% by weight of the aromatic vinyl monomer, 5 to 20% by weight of the monomer copolymerizable with the aromatic vinyl monomer, and processability And 20 to 50% by weight of the copolymer resin graft-polymerized by adding 0 to 15% by weight of the monomer which adds heat resistance, and (a ₂ ) 60 to 80% by weight of the aromatic vinyl monomer to be copolymerized with the aromatic vinyl monomer. (B) Bis to 100 parts by weight of a rubber-modified styrene resin composed of 40 to 20% by weight of a monomer and 80 to 50% by weight of a copolymer resin copolymerized by adding 0 to 30% by weight of a monomer that adds processability and heat resistance. 3 to 15 parts by weight of (2,3-dibromoethyl ether) tetrabromobisphenol A, (C) 0.5 to 5 parts by weight of the antimony compound, and (D) 0.001 to 0.2 parts by weight of the siloxane compound It is a flame-retardant resin composition excellent in Keel impact resistance. In the resin composition of the present invention, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye may be added according to each use.

Description

[Name of invention]

Thermoplastic resin composition having flame resistance excellent in impact resistance

Detailed description of the invention

[Field of Invention]

The present invention relates to a thermoplastic resin composition having flame retardancy excellent in impact resistance.

More specifically, the present invention provides a rubber-modified styrene resin composed of a graft copolymer resin and a copolymer resin, bis (2,3-dibromoethyl ether) tetrabromobistenol A, an antimony compound, and a siloxane compound as a flame retardant. It relates to a flame retardant thermoplastic resin composition having a good impact strength and workability made of a compound.

The thermoplastic resin composition according to the present invention may be added in the required amount of an inorganic additive, a heat stabilizer, an antioxidant, a dye or a pigment according to each use of the resin composition.

[Background of invention]

In general, rubber-modified styrene-based resin has good processability, excellent mechanical properties such as impact strength, and good appearance, and has been commonly used for various applications such as electrical appliances and office equipment. However, when used in a product that emits a lot of heat, such as personal computers, faxes, there is a disadvantage that there is a combustibility.

Therefore, in order to prevent this combustibility, a halogen-based compound is added to the rubber-modified styrene resin composition as a flame retardant, and has been used as a flame-retardant rubber-modified styrene resin composition. Usually, it is well known in the art that this halogen compound is used together with the antimony compound to impart UL 94 V-0 flame retardancy to the resin composition.

However, commercially available flame retardants which impart V-2 flame retardant properties to rubber modified styrene resin compositions are rare. Hexabromocyclododecane is known as a flame retardant, but this compound is not suitable for use in achromatic products because it is deteriorated due to thermal stability at a general processing temperature and is used only in achromatic resin products.

Therefore, the inventors of the present invention have solved the above problems with bis (2,3-dibromoethyl ether) tetrabromobisphenol A having better thermal stability than hexabromocyclododecane as a flame retardant of antimony-based compounds and rubber-modified styrene resins. By adding a siloxane-based compound which is used as a and minimizes the loss of impact strength, it has led to the development of a rubber-modified styrene resin composition that prevents the deterioration of mechanical properties and has excellent flame retardancy.

[Purpose of invention]

An object of the present invention is to provide excellent impact resistance by using bis (2,3-dibroethylethyl) tetrabromobisphenol A, an antimony compound, and a siloxane compound as an impact modifier in a rubber-modified styrene resin as a flame retardant. It is to provide a rubber-modified styrene-based flame retardant resin composition.

It is another object of the present invention to provide a rubber-modified styrene-based resin by using the compound bis (2,3-dibromoethylether) tetrabromobisphenol A as a flame retardant, an antimony compound, and a siloxane compound as an impact modifier. 2 It is to provide a rubber-modified styrene resin composition having flame retardant properties and excellent mechanical properties such as impact strength.

[Summary of invention]

The thermoplastic resin composition of the present invention (A) (a ₁ ) 35 to 65% by weight of the rubber polymer 30 to 50% by weight of the aromatic vinyl monomer, 5 to 20% by weight of the copolymerizable monomer with the aromatic vinyl monomer, and processability And 20 to 50 parts by weight of a copolymer resin graft-polymerized by adding 0 to 15% by weight of a monomer which adds heat resistance, and (a ₂ ) 60 to 80% by weight of an aromatic vinyl monomer to be copolymerized with the aromatic vinyl monomer. 100 parts by weight of a rubber-modified styrene resin comprising 40 to 20% by weight of a monomer and 80 to 50 parts by weight of a copolymer resin copolymerized by adding 0 to 30% by weight of a monomer that adds processability and heat resistance; (B) 3 to 15 parts by weight of bis (2,3-dibromoethyl ether) tetrabromobisphenol A; (C) 0.5 to 5 parts by weight of the antimony compound; And (D) 0.001 to 0.2 parts by weight of siloxane compound; It is a rubber-modified styrene flame-retardant resin composition excellent in impact resistance mixed with.

In the resin composition of the present invention, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye may be added according to each use.

Detailed Description of the Invention

The plastic resin composition of the present invention comprises (A) a rubber-modified styrene resin comprising a graft copolymer resin and a copolymer resin, (B) bis (2,3-dibromoethyl ether) tetrabromobisphenol A, (C) It consists of an antimony compound, and (D) siloxane compound. Description of each of these components is as follows.

[A. Rubber modified styrene resin]

Rubber-modified resin refers to a resin in which rubber-like polymers are dispersed in the form of particles in a matrix in which aromatic vinyl-based polymers are continuously present, and a method of manufacturing the aromatic-vinyl monomer in rubber-like polymers and optionally It adds and polymerizes the monomer copolymerizable with an aromatic vinylic monomer.

As the polymerization method of the rubber-modified styrene resin as described above, well-known methods in the art, such as emulsion polymerization, suspension polymerization, and bulk polymerization, may be used, and in the case of block polymerization, graft copolymer resin and copolymer resin are used. The rubber-modified styrene resin is produced only by one-step reaction without separately preparing the rubber-modified styrene resin, but in any case, it is suitable to maintain the rubber polymer content in the rubber-modified styrene resin at 10 to 30% by weight.

Typically, the rubber-modified styrene resin is produced by mixing and extruding graft copolymer resin and copolymer resin.

The rubber-modified styrenic resin used in the present invention may be prepared by using graft copolymer resin alone or in combination with graft copolymer resin and copolymer resin, and blended in consideration of their compatibility.

[a ₁ . Graft copolymer resin]

As a rubbery polymer used for manufacture of the graft copolymer resin of this invention, Diene type rubbers, such as polybutadiene, poly (styrene / butadiene), and poly (acrylonitrile / butadiene); Saturated rubber which added hydrogen to diene type rubber; Isoprene rubber; Chloroprene rubber; Acrylic rubbers such as butyl polyacrylate; And ethylene / propylene / diene monomer terpolymers (EPDM); Etc. Among them, the rubber polymer used in the present invention is preferably a diene rubber, and more preferably a butadiene rubber.

The content of the rubbery polymer is preferably added at 35 to 65% by weight of the graft copolymer resin. In addition, in preparing the graft copolymer of the present invention, in consideration of impact strength and appearance, the average size of the rubbery polymer particles is suitably in the range of 0.1 to 3 μm.

Aromatic vinyl monomers used in the graft copolymers of the present invention include styrene, α-methylstyrene, p-styrene chloride, p-brominated styrene, 2, 4, 5-tribrominated styrene, and the like. Among them, styrene is most preferred.

In the graft copolymer of the present invention, one or more monomers copolymerizable with the aromatic vinyl monomer may be introduced. The copolymerizable monomer is preferably a vinyl cyanide compound such as acrylonitrile or an unsaturated nitrile compound such as methacrylonitrile.

In the present invention, the graft copolymer total component rubbery polymer is 35 to 65% by weight, the aromatic vinyl monomer is 30 to 50% by weight, the copolymerizable monomer is added by 5 to 20% by weight graft copolymerization .

In order to impart properties such as processability and heat resistance when preparing the graft copolymer, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleade may be further added to graft polymerization. The amount added is in the range of 0 to 15% by weight of the graft copolymer resin as a whole.

[a2. Copolymer resin]

The copolymer resin of the present invention is prepared according to the ratio and compatibility of the components of the monomers except the rubbery polymer in the graft copolymer resin component. The component and ratio are as follows.

As the aromatic vinyl monomer to be copolymerized, styrene, α-methylstyrene, p-methylstyrene, p-styrene chloride, p-brominated styrene, and 2,4,5-tribrominated styrene may be used, among which styrene Is most preferred.

The amount of the aromatic vinyl monomer added in the total components of the copolymer resin is preferably 60 to 80% by weight.

One or more types of monomers copolymerizable with the aromatic vinyl monomers are introduced into the copolymer resin. The copolymerizable monomer is preferably a vinyl cyanide compound such as acrylonitrile or an unsaturated nitrile compound such as methacrylonitrile. The monomer is introduced at 40 to 20% by weight of the total component of the copolymer resin.

The copolymer resin may be copolymerized by adding 0 to 30% by weight of monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleade in order to impart properties such as processability and heat resistance.

Examples of the rubber-modified styrene resins described above include acrylonitrile / butadiene / styrene copolymer resins (ABS), acrylonitrile / ethylene propylene rubber / styrene copolymer resins (AES), acrylonitrile / acryl rubber / styrene copolymers. Resins (AAS) and high impact polystyrene resins (HIPS).

[B. Bis (2,3-dibromoethyl ether) tetrabromobisphenol A]

Bis (2,3-dibromoethylether) tetrabromobisphenol A used as a flame retardant in the present invention is a flame retardant having the following structural formula (I):

The compound is a bromine-containing compound, wherein the bromine content is 67 to 68 parts by weight.

Bis (2,3-dibromoethyl ether) tetrabromobisphenol A having the above structure has a characteristic that the melting point is in the range of 95 to 105 占 폚.

The bis (2,3-dibromoethyl ether) tetrabromobisphenol A is preferably added in an amount of 3 to 15 parts by weight based on 100 parts by weight of the rubber modified styrene resin.

[C. Antimony compound]

Typically, antimony compounds are used in combination with halogen compounds such as bis (2,3-dibromoethyl ether) tetrabromobisphenol A as flame retardants, resulting in the effect of increasing the flame retardancy in rubber modified styrene resins and the like.

As the antimony compound used in the present invention, antimony trioxide and antimony pentoxide are preferable.

The antimony compound is preferably added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the rubber modified styrene resin.

[D.siloxane compound]

In bis (2,3-dibromoethyl ether) tetrabromobisphenol A, rubber modified resins have been used as a flame retardant only for high impact polystyrene (HIPS), polystyrene, polyethylene, polypropylene, and polyurethane.

Bis (2,3-dibromoethylether) tetrabromobisphenol A is compatible with polystyrene, polyolefins and polyurethanes, and thus flame retardant thermoplastic resins having UV94 V-2 flame retardant properties with almost no deterioration in mechanical properties of the resins. Can be prepared.

However, when bis (2,3-dibromoethylether) tetrabromobisphenol A is used as a flame retardant in high-impact polystyrene or rubber-modified styrene resins except polystyrene, mechanical strength, particularly impact strength, is greatly reduced. Have.

In order to impart V-2 flame retardancy to the rubber-modified styrene resin, bis (2,3-dibromoethyl ether) tetrabromobisphenol A and an antimony compound for increasing flame retardancy are added, and a flame retardant and an antimony compound are added. Impact strength of the rubber-modified styrene resin is reduced to 30 to 40% of the conventional rubber-modified styrene resin. The reason is that the flame retardant and antimony-based compound act as a kind of impurity to the rubber-modified styrene-based resin, which lowers the mechanical strength, that is, it acts as a starting point of cracking when phenomena such as fracture occur. This is because the rubber reinforcing effect is halved as the brittleness is improved.

Therefore, when using bis (2,3-dibromoethyl ether) tetrabromobisphenol A as a flame retardant in a rubber modified styrene resin, an additive for minimizing the loss of impact strength of the resin is essential.

In the present invention, a siloxane compound having the following structural formula is used as the additive:

This siloxane compound consists of a siloxane bond (Si-O-Si) and an organic methyl group.

Typically, the siloxane compound is divided into various types according to the n value of the structural formula, that is, the degree of polymerization, and has the property of improving the lubricity of the polymer material, that is, lowering the surface tension.

When the siloxane compound is added, the ductility of the copolymer resin, which is a matrix, is sufficiently improved, thereby suppressing brittleness due to the addition of a flame retardant, and at the same time, imparting mutual lubrication between molecules to reduce the impact strength of the flame retardant and additives. It doesn't happen at all.

The siloxane compound which can be used in the present invention is preferably polydimethyl siloxane having the above formula (II), and n value in the above formula (II) is preferably in the range of 20 to 1000.

The siloxane compound is added in an amount of 0.001 to 0.2 parts by weight based on 100 parts by weight of the rubber modified styrene resin.

The thermoplastic resin composition of the present invention may be added with an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye according to each use. Inorganic additives to be added include asbestos, glass fibers, talc, ceramics, and the like.

The additives are added in the range of 0 to 30 parts by weight based on 100 parts by weight of the rubber modified styrene resin.

As described above, the thermoplastic resin composition of the present invention generally includes a rubber-modified styrene resin, a bis (2,3-dibromoethyl ether) tetrabromobisphenol A, an antimony compound, a siloxane compound, and an additive according to the use. After mixing in a mixer of to prepare a resin composition in the form of pellets through an extruder.

The thermoplastic resin composition having the composition of the present invention improves fluidity with addition of a flame retardant without causing a decrease in the mechanical strength of the rubber-modified styrene resin, and thus greatly improves workability.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

EXAMPLE

The compositions used in Examples 1 to 2 and Comparative Examples 1 to 4 may be (A) rubber modified styrene resins, (B) bis (2,3-dibromoethyl ether) tetrabromobisphenol A, (C ) Antimony-based compound, and (D) siloxane-based compound and their preparation method and specifications are as follows.

[A. Rubber modified styrene resin]

[a ₁ . Graft copolymer resin]

To the solids of butadiene rubber latex, 36 parts by weight of styrene, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water were added to 50 parts by weight of the solid, and 1.0 parts by weight of potassium oleate and 0.4 weight of cumene hydroperoxide were added to the total solids. Part, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, 0.3 parts by weight of pyrophosphate sodium salt and maintained at 75 ° C. for 5 hours to complete the reaction to obtain a graft copolymer (G- ABS) latex was prepared. 0.4 parts by weight of sulfuric acid was added to the resulting resin composition solid to solidify, thereby preparing a graft copolymer resin (G-ABS) in powder form.

[a ₂ . Copolymer resin]

Styrene was added by adding 75 parts by weight, 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.2 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, and 0.4 parts by weight of mercaptan-based chain transfer agent. Styrene / acrylonitrile copolymer resin (SAN) was prepared by raising the temperature from room temperature to 80 ° C. for 90 minutes and then holding at this temperature for 180 minutes. This was washed with water, dehydrated and dried to prepare a powdered styrene / acrylonitrile copolymer resin (SAN).

The weight average molecular weight of the synthesized styrene / acrylonitrile copolymer resin was about 90,000 to 100,000.

[B. Bis (2,3-dibromoethyl ether) tetrabromobisphenol A]

The brand name FCF-680G of Sujihiro Chemical Co., Ltd., Japan, was used. The compound had a purity of 94% or more and a melting point of 105 ° C.

[C. Antimony compound]

The antimony trioxide of Korea's First Fire Retardant was used.

[D. Siloxane compound]

The brand name KF96-100 of Shin-Etsu Co., Ltd., the thing of 100cps in 25 degreeC was used.

[Examples 1-2 and Comparative Examples 1-4]

The composition of each component used in Examples 1-2 and Comparative Examples 1-4 is shown in Table 1. Examples 1 to 2 are examples according to the resin composition of the present invention. Examples 1 and 2 are compositions in which the component ratios of G-ABS, SAN, and bis (2,3-dibromoethyl ether) tetrabromobisphenol A are slightly differently applied. Comparative Examples 1 to 3 are resin compositions prepared by applying the rubber-modified styrene resin of Example 1 and applying a flame retardant and an additive to each of them. Comparative Example 4 is a resin composition prepared by applying the rubber modified styrene resin of Example 2 and without adding an additive (siloxane compound).

Each component in Examples 1-2 and Comparative Examples 1-4 was mixed and extruded in the extruder, and the pellet-like resin composition was manufactured.

TABLE 1

The impact strength, flowability, and flame retardance of the test pieces of the resin composition prepared according to Examples 1 to 2 and Comparative Examples 1 to 4 were measured. The results are shown in Table 2. The evaluation method for the physical properties was measured according to the following conditions.

(1) Impact strength (kgfcm / cm): Notched impact strength was measured according to ASTM D-256 conditions.

(2) Flowability (g / 10 min): measured at 200 ° C. and 5 kgf load according to ASTM D-1238 conditions.

(3) Flame retardant: measured according to UL94 VB flame retardant standard.

TABLE 2

As can be seen from Table 2, the compositions prepared according to Examples 1 to 2 of the present invention was excellent in flame retardancy UL94 V-2, showing a very good result of balance of both impact strength and flow.

Looking at the results of Comparative Examples 1 to 3 compared with Example 1, Comparative Example 1 corresponds to a control (control) which is a resin composition consisting only of rubber-modified styrene-based and could not secure the flame retardancy of V-2. In Comparative Example 2, the siloxane compound was added to Comparative Example 1, which is a control, and the flame resistance of V-2 could not be secured, but the impact strength of the resin composition was improved (14 → 20). In Comparative Example 3, a flame retardant, i.e., bis (2,3-dibromoethyl ether) tetrabromobisphenol A and an antimony trioxide compound was added to the control, thereby securing V-2 flame retardancy, but the impact strength was sharply decreased compared to the control ( 14 → 6).

Comparative Example 4 The same result as in Comparative Example 3 was obtained.

Therefore, it was confirmed that Examples 1 to 2, which are the resin composition of the present invention, not only impart flame retardancy to existing rubber-modified styrene resins but also improve impact strength and flowability.

Simple modifications or variations of the present invention can be readily made by those skilled in the art, and all such modifications or changes can be seen to be included within the scope of the present invention.

Claims (5)

(A) (a ₁ ) From 30 to 50% by weight of an aromatic vinyl monomer, from 5 to 20% by weight of a monomer copolymerizable with the aromatic vinyl system, and from 0 to 35 monomers which adds processability and heat resistance to 35 to 65% by weight of the rubbery polymer. 20 to 50% by weight of graft copolymer resin graft-polymerized by adding 15% by weight, and (a2) 60 to 80% by weight of an aromatic vinyl monomer capable of copolymerizing with the aromatic vinyl monomer. 100 weight part of rubber-modified styrene resins which consist of 80 to 50 weight% of copolymer resins copolymerized by adding the weight% and 0-30 weight% of the monomer which adds workability and heat resistance; (B) 3 to 15 parts by weight of bis (2,3-dibromoethyl ether) tetrabromobisphenol A represented by the following general formula (I) with respect to 100 parts by weight of the rubber-modified styrene resin; (C) 0.5 to 5 parts by weight of the antimony compound based on 100 parts by weight of the rubber-modified styrene resin; And (D) 0.001 to 0.2 parts by weight of siloxane compound based on 100 parts by weight of the rubber-modified styrene resin; A thermoplastic resin composition having flame retardancy excellent in impact resistance, characterized by comprising. According to claim 1, wherein the rubber polymer (a ₁ ) is a diene rubber, a saturated rubber added hydrogen to the diene rubber, isoprene rubber, chloroprene rubber, acrylic rubber and ethylene / propylene / diene monomer terpolymer ( EPDM); The aromatic vinyl monomer (a ₁ , a ₂ ) is selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, p-styrene chloride, p-bromide styrene, and 2,4,5-tribromide styrene Being; The monomer copolymerizable with the aromatic vinyl monomer is selected from vinyl cyanide and unsaturated nitrile compounds; Monomers (a ₁ , a ₂ ) adding the processability and heat resistance are selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleade; And the antimony-based compound is antimony trioxide or antimony pentoxide, the thermoplastic resin composition having excellent flame resistance. The method of claim 1, wherein the rubber modified styrene resin (A) is acrylonitrile / butadiene / styrene copolymer resin (ABS), acrylonitrile / acrylic rubber / styrene copolymer resin (AAS), acrylonitrile / ethylene A thermoplastic resin composition having excellent flame resistance, characterized in that it is selected from the group consisting of propylene rubber / styrene copolymer resin (AES) and high impact polystyrene resin (HIPS). The thermoplastic resin composition according to claim 1, wherein the siloxane compound (D) is polydimethyl siloxane of the following structural formula. The thermoplastic resin composition of claim 1, wherein the resin composition further comprises an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye.