KR20090054487A - Flame retardant thermoplastic resin composition having good detergent resistance and improved impact strength - Google Patents

Abstract

A flame retardant thermoplastic resin composition is provided to secure excellent detergent resistance, shock resistance, processability, mechanical strength, thermal stability and fire retardant characteristic and to be applied to bath supplies, laundry products, interiors for a washing machine. A flame retardant thermoplastic resin composition comprises (A) rubber-modified aromatic vinyl cyanide vinyl grafted copolymer resin 100.0 parts by weight; (B) chlorinated polyvinyl-based polymer 3~40 parts by weight; (C) halogenated flame retardant 5~30 parts by weight; and (D) antimony oxide 1~15 parts by weight. The rubber-modified aromatic vinyl cyanide vinyl grafted copolymer resin(A) is an acrylonitrile-butadiene-styrene copolymer. The chlorinated polyvinyl-based polymer(B) is selected from chlorinated polyethylene, polyvinylchloride, chlorinated polyethylene-polypropylene copolymer, chlorinated polyethylene-polyacrylate copolymer and their mixture.

Description

Flame Retardant Thermoplastic Resin Composition Having Good Detergent Resistance and Improved Impact Strength}

Field of invention

The present invention relates to a flame retardant thermoplastic resin composition excellent in impact resistance and detergent resistance. More specifically, the present invention relates to a flame retardant thermoplastic resin composition in which a chlorinated polyvinyl polymer is applied to a rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin to improve impact resistance as well as detergent resistance.

Background of the Invention

In general, styrene-based resins are widely used in the manufacture of interior and exterior parts, such as electrical and electronic products and office automation equipment because of their excellent processability and mechanical strength and their excellent appearance.

However, styrene-based resins are not resistant to combustion in themselves, and when a spark is ignited by an external ignition factor, the resin itself acts as an energy to assist combustion, thereby continuously spreading fire. Therefore, in order to secure safety against fires in electric and electronic products, it is a trend to legalize the use of flame retardant resins in internal and external parts of electric and electronic products.

There are various methods for imparting flame retardancy to styrene resins. Among them, an additional flame retardant method in which an organic compound containing halogen is used as a flame retardant and an inorganic compound containing antimony oxide is added thereto as a flame retardant aid is commercialized. As the halogen-containing organic compound, bromine compounds are mainly used. However, when the bromine compound is added to the styrene resin, the flame retardancy of the styrene resin is greatly improved, while the overall physical properties of the resin itself, such as thermal stability, impact strength, weather resistance, heat resistance, and workability, are severely degraded. There are disadvantages. Accordingly, it is necessary to develop a styrene resin having excellent flame resistance and excellent balance of physical properties such as impact resistance.

On the other hand, recently, the use of flame retardant styrene resins for household goods, bathroom products, etc. is increasing, and in particular, the development of styrene resins having resistance to alkali detergents as well as flame retardant, fluidity and impact resistance properties, is required. It is becoming.

Accordingly, the present inventors apply chlorinated polyvinyl-based polymers, halogen-based flame retardants and antimony oxide to rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resins, which are excellent in impact resistance and detergent resistance and require resistance to alkaline detergents. To develop a flame retardant thermoplastic resin composition that can be applied to laundry, kitchen products, and the like.

An object of the present invention is to provide a detergent resistant flame retardant thermoplastic resin composition excellent in the resistance of the alkaline detergent.

Another object of the present invention is to provide a detergent resistant flame retardant thermoplastic resin composition having excellent mechanical strength, thermal stability and flame retardancy simultaneously.

Another object of the present invention is to provide a detergent-resistant flame retardant thermoplastic resin composition excellent in processability.

Still another object of the present invention is to provide a flame retardant thermoplastic resin composition which can be applied to bathroom articles, laundry products, kitchen utensils, etc., having excellent detergent and impact resistance and requiring resistance to alkaline detergents.

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

Summary of the Invention

The resin composition of the present invention (A) 100 parts by weight of rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin; (B) 3 to 40 parts by weight of chlorinated polyvinyl polymer; (C) 5 to 30 parts by weight of halogen-based flame retardant; And (D) 1 to 15 parts by weight of antimony oxide.

In one embodiment, the rubber modified aromatic vinyl-vinyl cyanide graft copolymer resin (A) is an acrylonitrile-butadiene-styrene copolymer (ABS) resin.

As the chlorinated polyvinyl polymer (B), chlorinated polyethylene (CPE), polyvinyl chloride (PVC), chlorinated polyethylene-polypropylene copolymer, chlorinated polyethylene-polyacrylate copolymer, or a mixture thereof may be used. .

In a specific embodiment of the present invention, the chlorinated polyethylene (CPE) has a specific gravity of 1.1 to 1.3 and a chlorine content of 30 to 50% by weight.

The halogen flame retardant (C) is tetrabromobisphenol A (bis) (tribromophenoxy) ethane (tribromophenoxy) ethane (brominated epoxy resin), epoxy terminal is tribromo Brominated epoxy resin terminated with tribromophenol or mixtures thereof may be used.

The antimony oxide (D) may be used antimony trioxide, antimony pentoxide or a mixture thereof.

In this invention, the molded article which shape | molded the said resin composition is included. The molded article may be preferably applied to bathroom articles, laundry products, interior materials for washing machines, and the like, which need resistance to alkali detergents.

Detailed Description of the Invention

(A) Rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin

In the present invention, the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A) is prepared by mixing a rubber, an aromatic vinyl monomer, and a vinyl cyanide monomer, and thermally polymerizing or graft-polymerizing it using a polymerization initiator. Can be.

In one embodiment, the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A) is a polymer of 5 to 30% by weight of a vinyl cyanide compound, 5 to 30% by weight of a rubber polymer and 40 to 90% by weight of an aromatic vinyl compound. .

In a specific embodiment of the present invention, the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A) is a graft copolymer (a1) 5 to obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound together with a rubber polymer. It is composed of 0 to 95% by weight of copolymer (a2) obtained by copolymerizing 100% by weight, preferably 10 to 30% by weight of an aromatic vinyl compound and a vinyl cyanide compound, preferably 70 to 90% by weight.

The graft copolymer (a1) is 4 to 30% by weight of the rubber polymer, 30 to 95% by weight of the aromatic vinyl compound, and 1 to 40% by weight of the vinyl cyanide compound to be graft copolymerized.

The copolymer (a2) is a copolymer of 20 to 40% by weight of a vinyl cyanide compound and 60 to 80% by weight of an aromatic vinyl compound. The weight average molecular weight of the copolymer (a2) is preferably in the range of 80,000 to 200,000. When the weight average molecular weight is in the above range, it is more preferable to prevent unmolding, gas generation defects, etc. in the injection molding of a complicated large structure because of excellent balance of physical properties such as impact resistance, heat resistance and flowability.

The rubber is a butadiene rubber, a copolymer of butadiene and styrene, a diene rubber such as poly (acrylonitrile-butadiene), a saturated rubber hydrogenated with the diene rubber, isoprene rubber, an acrylic rubber, an ethylene-propylene rubber, ethylene -Propylene-diene monomer terpolymer (EPDM), silicone rubber and the like can be used. Preferably, polybutadiene, a copolymer of butadiene and styrene, isoprene rubber, alkyl acrylate rubber and the like are used. The content of the rubber is suitably 3 to 30% by weight, preferably 5 to 20% by weight of the total weight of the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin.

As said aromatic vinyl compound, styrene, such as styrene, (alpha) -methylstyrene, (beta) -methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichloro styrene, dibromostyrene, etc. System monomers may be used, but are not necessarily limited thereto. The aromatic vinyl compound may be used alone or in combination of two or more thereof, of which styrene is most preferred.

Acrylonitrile, methacrylonitrile, or the like may be used as the vinyl cyanide compound, and these may be used alone or in combination of two or more thereof. Most preferred is double acrylonitrile.

The rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin of the present invention may be copolymerized by adding acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like as necessary.

The rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin of the present invention is acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-ethylenepropylene rubber-styrene copolymer resin (AES), acrylonitrile -Acrylic rubber-styrene copolymer resin (AAS) and the like, and preferably acrylonitrile-butadiene-styrene copolymer resin (ABS).

(B) Chlorinated Polyvinyl Polymer

In the present invention, the chlorinated polyvinyl polymer (B) is used as a flame retardant aid and impact modifier.

The chlorinated polyvinyl polymer refers to a vinyl polymer containing chlorine due to substitution or addition of chlorine.

Examples of the chlorinated polyvinyl polymer (B) include chlorinated polyethylene (CPE), polyvinyl chloride (PVC), chlorinated polyethylene-polypropylene copolymers, chlorinated polyethylene-polyacrylate copolymers, and the like. The use of chlorinated polyethylene (CPE) is more preferable in terms of price and physical properties.

The chlorinated polyethylene is chlorinated by the substitution reaction of the high density polyethylene through the bulk polymerization, the properties are dependent on the chlorine content, chlorine dispersion and the nature of the high density polyethylene.

In one embodiment of the present invention, the chlorine content of the chlorinated polyethylene may be substituted with 20 to 60% by weight, preferably 30 to 50% by weight is substituted. Further, the chlorinated polyethylene has a specific gravity of 1.0 to 1.4, preferably 1.1 to 1.3.

In the present invention, the chlorinated polyvinyl polymer (B) is 3 to 40 parts by weight, preferably 10 to 40 parts by weight with respect to 100 parts by weight of the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A). Used. If the chlorinated polyvinyl-based polymer (B) is less than 3 parts by weight, sufficient flame retardant auxiliary effect and detergent resistance against alkali and high impact strength cannot be obtained, and if it exceeds 40 parts by weight, thermal stability may be significantly reduced.

(C) halogen-based flame retardant

In the present invention, the halogen-based flame retardant is to impart flame retardancy, and commercially available halogen-based compounds may be used.

The halogen flame retardant may be used, such as chlorinated flame retardant or brominated flame retardant, brominated flame retardant is usually applied.

Specific examples of the flame retardant include tetrabromobisphenol A, bibro (tribromophenoxy) ethane, brominated epoxy resin, and epoxy bromide tribromophenol. Brominated epoxy resin (brominated epoxy resin terminated with tribromophenol) and the like, for example, but is not limited thereto. The halogen flame retardant may be used alone or in combination of two or more.

In the present invention, the halogen-based flame retardant (C) is used in an amount of 5 to 30 parts by weight, preferably 10 to 25 parts by weight with respect to 100 parts by weight of the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A). desirable. If the amount is less than 5 parts by weight, sufficient flame retardant effect may not be obtained. If the amount is more than 30 parts by weight, workability and mechanical strength may be lowered, and thus the balance of physical properties of the resin composition may be broken.

(D) antimony oxide

In the present invention, antimony oxide (D) synergizes with the halogen-based compound (C) used as a flame retardant to impart proper flame retardancy to the thermoplastic resin of the present invention.

Examples of the antimony oxide (D) include antimony trioxide or antimony pentoxide, but antimony trioxide is more preferable in terms of price and physical properties, but is not limited thereto. The antimony oxide (D) may be used by mixing antimony trioxide and antimony pentoxide.

The amount of the antimony oxide used is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight based on 100 parts by weight of the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A). If the amount is less than 1 part by weight, sufficient flame retardant effect may not be obtained. If the amount is more than 20 parts by weight, the balance of physical properties of the resin composition may be broken.

In the present invention, if necessary, conventional additives such as tin maleate compounds, aluminosilicate compounds, waxes, metal lubricants, antioxidants, light stabilizers, inorganic fillers, pigments, and dyes may be further included. The conventional additives may be used alone or in combination of two or more thereof. The tin maleate-based compound or aluminosilicate-based inorganic compound serves as a flame retardant heat stabilizer to prevent discoloration of the resin composition by acting as a halogen capture when using a halogen-based flame retardant. The amount of the additive may further include 30 parts by weight or less based on 100 parts by weight of the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A).

The resin composition of this invention can be manufactured by a well-known method. For example, after mixing the components of the present invention, it can be melt extruded in an extruder and made into pellets. In one embodiment, a tinmalate compound or an aluminosilicate inorganic compound, an antioxidant, a metal lubricant, a wax, titanium dioxide, benzotriazole, and a hindered amine light stabilizer are added to each of the components as a halogen capture. It is mixed in a conventional mixer, and the mixture is extruded through an extruder to prepare a resin composition in pellet form.

The composition of the present invention is very excellent in mechanical strength, thermal stability, moldability, flame retardancy and detergent resistance, it can be used in the molding of various products. In particular, it is widely applicable to bathroom accessories, laundry products, washing materials, washing utensils, kitchen containers, children's toys, etc., which need resistance to alkali detergents. For example, it can be preferably applied to a variety of bathroom products, such as bathroom shoes, bathroom cabinet, scaffolding, wash basin, soap case, detergent container.

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 specifications of (A) ABS resin, (B) chlorinated polyvinyl compound, (C) halogen compound, and (D) antimony oxide used in the following Examples and Comparative Examples are as follows. Halogen-based compounds, antimony oxide, chlorinated polyvinyl-based compounds, and other additives were used as such without commercially available products.

(A) Rubber modified aromatic vinyl-vinyl cyanide graft copolymer resin (ABS resin)

30 parts by weight of g-ABS resin (PBD CONTENT: 58 wt%, styrene 31.5 wt%, acrylonitrile content 10.5 wt%) prepared by graft polymerization using butadiene rubber having an average particle diameter of 0.30 μm and a weight average molecular weight An ABS resin having a butadiene rubber content of 17,800 wt% was prepared using 70 parts by weight of a styrene-acrylonitrile copolymer (SAN) resin having 88,000, an acrylonitrile content of 28 wt% and a styrene content of 72 wt%. .

(B) Chlorinated Polyvinyl Compound

Chlorinated polyethylene (CPE) Tyrin 3245P (DDE, USA) was used.

(C) halogen-based compound

TBBA-based flame retardant SAYTEX RB 100 (ALBERMALE, USA) having a weight average molecular weight of 550 was used.

(D) antimony oxide

Antimony trioxide (ILS antimony, Korea) was used.

Example 1

Each component is added as shown in Table 1 below, and 1 part by weight of tin maleate compound TM-600P (Songwon Industrial Co., Korea) as a halogen capture, Irganox 1076 (Songwon Industrial Co., Ltd.) as a hindered phenolic antioxidant as an antioxidant Korea) 0.3 parts by weight, stearic acid-based metal lubricant SONGSTAB Ca-ST (Songwon Industrial Co., South Korea) 0.4 parts by weight and 1 part by weight of wax is mixed uniformly with a mixer, L / D = 35, Φ = 45mm After extruding at a temperature of 240 ° C. using a twin screw extruder, the extrudate was prepared in pellet form. The prepared pellets were dried for at least 5 hours in a hot air dryer at 80 ℃ before injection.

Example 2

Except for using 10 parts by weight of the chlorinated polyvinyl compound was carried out in the same manner as in Example 1.

Example 3

Except for using 20 parts by weight of the chlorinated polyvinyl compound was carried out in the same manner as in Example 1.

Example 4

Except for using 30 parts by weight of the chlorinated polyvinyl compound was carried out in the same manner as in Example 1.

Example 5

Except for using 40 parts by weight of the chlorinated polyvinyl compound was carried out in the same manner as in Example 1.

Comparative Example 1

The same procedure as in Example 1 was conducted except that no chlorinated polyvinyl compound was used.

Comparative Example 2

The same procedure as in Example 1 was carried out except that 2 parts by weight of a chlorinated polyvinyl compound was used.

Comparative Example 2

The same procedure as in Example 1 was carried out except that 45 parts by weight of chlorinated polyvinyl compound was used.

From the pellets prepared above, specimens for physical properties and flame retardancy test were prepared by injection molding. The measurement method for each property item was experimentally evaluated based on the following test analysis criteria.

(1) Impact strength measurement: 1/8 inch thickness was evaluated by ASTM D-256 test method, the unit is kgf · cm / cm.

(2) Fluidity: It was evaluated under the condition of 200 ℃ and 5 kg load by ASTM D-1238 test method, the unit is g / 10min.

(3) Hot softening point temperature: The test method of ASTM D1525 was evaluated under the condition of 50 / hr at 5 kg load, the unit is ℃.

(4) Flame retardancy measurement: According to the UL-94 flame retardancy determination test method, it was determined by testing about 1/12 inch thickness.

(5) Detergent resistance measurement: Detergent resistance is manufactured by making a test fixture for the detergent resistance, making a test piece with an injection molding, cutting the test piece to a certain standard (thickness 3.0mm × width 50mm × length 200mm) and annealing in an oven at 60 ℃ for 3 hours. After annealing, the test fixture was fixed and a conventional alkaline detergent (pH: 8-14) was applied. After applying the detergent, the detergent was continuously applied in the same amount at 5 hour intervals for a total of 48 hours, and then the presence of cracks caused by the detergent was measured (◎: no crack, ○: fine crack, ×: crack occurrence ). In addition, the crack incidence distance was measured from the larger critical elongation. At this time, the jig used is a critical elongation of 0.5%, and the critical elongation is distinguished from the larger elongation, not the jig which is equally applied to the critical elongation as in the general 1/2 ellipse method. Cracks do not occur, or the shorter the distance generated is excellent detergent resistance, the measurement results for each property item are shown in Table 2 below.

As shown in Table 2, in Examples 1 to 5 in which chlorinated polyethylene is applied in a constant content, it can be confirmed that the present invention has excellent impact strength, fluidity, flame retardancy, and detergent resistance. On the other hand, Comparative Example 1-2, which does not use chlorinated polyethylene or is added in a small amount, it can be seen that the impact resistance, fluidity, flame retardancy and detergent resistance are all reduced. In addition, in Comparative Example 3 in which an excessive amount of chlorinated polyethylene was added, it was confirmed that the impact strength was significantly reduced.

The present invention has excellent detergent resistance, impact resistance, and workability, and at the same time secures mechanical strength, thermal stability, and flame retardancy, flame retardant thermoplastic resin composition that can be applied to bathroom articles, laundry products, interior materials for washing machines, etc. requiring resistance to alkali detergents. It has the effect of providing the invention.

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

Claims (9)

(A) 100 parts by weight of rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin; (B) 3 to 40 parts by weight of chlorinated polyvinyl polymer; (C) 5 to 30 parts by weight of a halogen flame retardant; And (D) 1 to 15 parts by weight of antimony oxide; Flame retardant thermoplastic resin composition excellent in impact resistance and detergent resistance. The flame retardant thermoplastic resin having excellent impact resistance and detergent resistance according to claim 1, wherein the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A) is an acrylonitrile-butadiene-styrene copolymer (ABS) resin. Resin composition. The polymer of claim 1, wherein the rubber-modified aromatic vinyl-vinyl cyanide graft copolymer resin (A) is a polymer of 5 to 30% by weight of a vinyl cyanide compound, 5 to 30% by weight of a rubber polymer and 40 to 90% by weight of an aromatic vinyl compound. Flame retardant thermoplastic resin composition excellent in impact resistance and detergent resistance. The method of claim 1, wherein the chlorinated polyvinyl polymer (B) is chlorinated polyethylene (CPE), polyvinyl chloride (PVC), chlorinated polyethylene-polypropylene copolymer, chlorinated polyethylene-polyacrylate copolymer and Flame retardant thermoplastic resin composition excellent in impact resistance and detergent resistance, characterized in that selected from the group consisting of. The flame retardant thermoplastic resin composition having excellent impact resistance and detergent resistance according to claim 4, wherein the chlorinated polyethylene (CPE) has a specific gravity of 1.1 to 1.3 and a chlorine content of 30 to 50 wt%. According to claim 1, wherein the halogen-based flame retardant (C) is tetrabromobisphenol A (tetrabromobisphenol A), bis (tribromophenoxy) ethane (tribromophenoxy) ethane, brominated epoxy resin (brominated epoxy resin), A flame-retardant thermoplastic resin composition excellent in impact resistance and detergent resistance, characterized in that the epoxy terminal is selected from the group consisting of brominated epoxy resin terminated with tribromophenol and mixtures thereof. The flame retardant thermoplastic resin composition having excellent impact resistance and detergent resistance according to claim 1, wherein the antimony oxide (D) is antimony trioxide, antimony pentoxide, or a mixture thereof.  The method of claim 1, wherein the resin composition further comprises at least one material selected from the group consisting of tin maleate compounds, aluminosilicate compounds, waxes, metal lubricants, antioxidants, light stabilizers, inorganic fillers, pigments and dyes. Flame retardant thermoplastic resin composition excellent in impact resistance and detergent resistance.  The molded article of the resin composition of any one of Claims 1-8.