KR20020007814A - Thermoplastic Flameproof Resin Composition - Google Patents

Abstract

PURPOSE: A thermoplastic fire retardant resin composition is provided, which is excellent in fire retardance and fire resistance by using SAN copolymer resin containing 5 to 18 wt% of acrylonitrile as a compatibilizer and carboxy phosphinic acid compound and phosphoric ester as a fire retardant in the preparation of fire retardant resin composed of rubber-reinforced SAN copolymer resin and polyphenylene ether. CONSTITUTION: The thermoplastic fire retardant resin composition comprises (A) 40 to 95 wt% of rubber-reinforced SAN copolymer of (a1) 20 to 100 wt% of SAN graft copolymer composed of 10 to 60 wt% of rubber and 90 to 40 wt% of SAN copolymer, and (a2) 80 to 0 wt% of SAN copolymer, in which the contents of acrylonitrile is 18 to 50 wt% in the ingredients excluding rubber; (B) 5 to 60 wt% of polyphenylene ether resin, in which the sum of (A) and (B) is 100; (C) 2 to 30 wt% (based on the total 100 wt% of (A) and (B)) of SAN copolymer having the acrylonitrile contents of 5 to 18 wt%; (D) 0.5 to 20 wt% (based on the total 100 wt% of (A) and (B)) of carboxy phosphinic acid compound represented by formula 1; and (E) 0 to 30 wt% (based on the total 100 wt% of (A) and (B)) of aromatic phosphoric ester compound represented by formula 2. In the formula 1, R1 is hydrogen, a C1-C12 alkyl group or a C6-C15 aryl group, which can be substituted with an alkyl group; and R2 is a C1-C12 alkylene group, a C1-C12 cycloalkylene group or C6-C15 aryl group which can be substituted with an alkyl group and in the formula 2, R3, R4, and R5 are independently a hydrogen or a C1-C4 alkyl group; X is a C6-C20 aryl group which can be substituted alkyl group and is one derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A or bisphenol-S; and m is an integer of 0 to 4.

Description

Thermoplastic Flameproof Resin Composition

Field of invention

The present invention relates to a thermoplastic flame retardant resin composition. More specifically, the present invention is an acrylonitrile content that is a compatibilizer in a SAN graft copolymer alone or in a base resin composed of a rubber-modified SAN copolymer resin composed of a SAN graft copolymer and a SAN copolymer resin and a polyphenylene ether resin. The present invention relates to a thermoplastic resin composition to which 5 to 18% by weight of a SAN copolymer resin and a carboxy phosphonic acid and an aromatic phosphate ester which are flame retardants are applied.

Background of the Invention

Rubber modified styrene resins have been widely applied to various applications such as electrical appliances and office equipment because of their good processability, excellent physical properties and good appearance. However, in general, when styrene resins are applied to heat dissipating products such as personal computers or fax machines, resins that have been provided with flame retardancy due to the combustibility of resins have been used. The most widely used flame retardant method is to impart flame retardant properties by applying a halogen-based compound and an antimony-based compound in combination to the rubber-modified styrene resin. However, halogen-containing compounds can cause fatal effects on the hydrogen halide gas generated during processing, and polybrominated diphenyl ether, the main component of halogen-based flame retardants, generates very toxic gases such as dioxins and furans during combustion. Because of the high possibility, attention has recently been focused on flame-retardant methods that do not apply halogen-based compounds.

The method of imparting flame retardancy to the resin composition by adding a compound containing phosphorus or nitrogen as a compound that does not contain halogen has been studied. However, when the phosphorus compound is used alone, the heat resistance of the rubber-modified styrene resin is lowered and the flame retardancy is insufficient. There is a disadvantage in that the application is limited.

In general, rubber-modified styrene-based resins, particularly acrylonitrile-butadiene-styrene copolymer resins (hereinafter referred to as ABS resins) have a disadvantage in that it is difficult to expect a flame retardant effect in a solid phase because there is little char remaining during combustion. of Applied Polymer Science, 1998, vol 68, p1067) Therefore, it is necessary to add a char forming agent so that the char can be generated smoothly to obtain desired flame retardancy.

According to Japanese Patent Application Laid-Open No. 7-48491, thermoplastic resins are applied by applying phosphate esters as flame retardants to thermoplastic copolymer resins such as high molecular weight polymers and aromatic vinyl monomers, and adding phenolic resins of Novolac type as char forming agents. A flame retardant resin was prepared. However, the phenol resin not only lowers the heat resistance of the styrene resin, but also has a disadvantage in that the heat resistance is further lowered because a relatively large amount of phosphate ester and novolak resin must be added to obtain the desired flame retardancy due to the lack of char forming ability. Have

Therefore, the present inventors use a rubber-modified SAN copolymer resin and a polyphenylene ether resin as the base resin to improve the flame retardancy of the styrene resin without using a phenol resin, and improve the compatibility of the two resin blends to improve thermal stability and In order to improve the flame retardancy, a SAN copolymer resin having an acrylonitrile content of 5 to 18 wt% is used as a compatibilizer, and a flame retardant thermoplastic resin is developed using an aromatic phosphate ester compound as a flame retardant, and has already applied for a patent.

In this invention, flame retardance is effectively given to resin by using carboxy phosphonic acid together as a flame retardant here. When carboxy phosphinic acid is used in combination with an aromatic phosphate ester compound, it forms a harder char film to block contact with heat and resin and to block the supply of combustion fuel, thereby providing a resin composition having excellent flame retardancy of UL 94 V-0. It is.

An object of the present invention is to provide a thermoplastic resin composition with improved flame retardancy by applying carboxy phosphinic acid to the existing resin composition.

Another object of the present invention is to provide a flame retardant thermoplastic resin composition having improved heat resistance.

It is another object of the present invention to produce a flame retardant resin of a rubber-modified SAN copolymer resin and a polyphenylene ether blend containing no harmful halogen, and having a acrylonitrile content of 5 to 18% by weight as a compatibilizer. The present invention provides a resin composition excellent in flame retardancy by applying and using a carboxy phosphinic acid and an aromatic phosphate ester compound as a flame retardant.

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

Hereinafter, the content of the present invention will be described in detail.

The thermoplastic flame-retardant resin composition of the present invention is (A) (a ₁ ) 20 to 100% by weight of SAN graft copolymer resin consisting of 10 to 60% by weight of the rubber component and 90 to 40% by weight of SAN copolymer resin and (a ₂ ) Rubber modified SAN copolymer resin composed of 80 to 0 wt% of SAN copolymer resin, 40 to 95 parts by weight of rubber modified SAN copolymer resin having an acrylonitrile content of 18 to 50 wt% And (B) a SAN copolymer having a content of (C) acrylonitrile of 5 to 18% by weight, based on 100 parts by weight of the base resin (A) + (B), which is composed of 5 to 60 parts by weight of a polyphenylene ether resin. It is characterized by consisting of 2-30 weight part of resin, 0.5-20 weight part of (D) carboxy phosphonic acid compounds, and 0-30 weight part of (E) aromatic phosphate ester compounds. That is, the resin composition of the present invention has very excellent flame retardancy compared to conventional thermoplastic resins by applying the carboxy phosphinic acid compound alone or together with the carboxy phosphinic acid compound and the aromatic phosphate ester compound as a flame retardant.

Hereinafter, each component of the resin composition of the present invention will be described in detail.

(A) Rubber-Modified SAN Copolymer Resin

Rubber-modified SAN copolymer resin refers to a polymer in which a rubbery polymer is dispersed in the form of particles in a matrix (continuous phase) made of a vinyl aromatic polymer, and can be copolymerized with an aromatic vinyl monomer in the presence of a rubbery polymer and a vinyl. It is superposed | polymerized by adding a system monomer. Such rubber-modified SAN copolymer resin can be prepared by known polymerization methods such as emulsion polymerization, suspension polymerization, and bulk polymerization, and are usually produced by mixing and extruding SAN graft copolymer resin and SAN copolymer resin. In the case of bulk polymerization, rubber modified SAN copolymer resin is produced by one step reaction process without graft copolymer resin and copolymer resin separately, but in all cases, the rubber content of the final rubber modified SAN copolymer resin component 5-30 parts by weight of the total is suitable. Examples of such resins include acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-acryl rubber-styrene copolymer resins (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymer resins, and the like. .

The resin may be applied alone or in combination of graft copolymer resin and copolymer resin, and is preferably blended in consideration of their compatibility.

(a ₁ ) SAN (styrene-acrylonitrile) graft copolymer resin

Examples of the rubber used for the graft copolymer resin include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and saturated rubber and isoprene which hydrogenated to the diene rubber. Although acrylic rubbers, such as rubber, a chloroprene rubber, and polybutylacrylic acid, ethylene-propylene-diene monomer terpolymer (EPDM), etc. can be mentioned, A diene rubber is preferable, More preferably, butadiene rubber is preferable. Suitable. The content of rubber is suitably 10 to 60% by weight in 100% by weight of the graft copolymer resin.

As the aromatic vinyl monomer in the graft polymerizable monomer mixture, styrene, α-methylstyrene, p -methylstyrene, and the like may be added, but styrene is most preferable, and a monomer copolymerizable with the aromatic vinyl monomer may be added thereto. Apply by introducing at least one. As the monomer which can be introduced, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile are preferable.

The weight ratio of rubber in the graft copolymer as a whole component is 10 to 60% by weight. The component of the monomer grafted to the rubber is 50 to 82% by weight of an aromatic vinyl monomer such as styrene, 18 to 50% by weight of an unsaturated nitrile monomer, and graft copolymerized monomer is applied. Further, in order to impart properties such as workability and heat resistance, monomers such as acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide may be added and graft polymerization. The amount added may be 0 to 40 parts by weight based on the total graft resin.

When preparing the graft copolymer, in consideration of impact strength and appearance, the average particle diameter of the rubber particles is preferably in the range of 0.1 to 4 μm.

(a ₂ ) SAN (styrene-acrylonitrile) copolymer resin

SAN copolymer resin is applied as needed in manufacturing the rubber-modified SAN copolymer resin, and the components thereof are as follows.

As the aromatic vinyl monomer to be copolymerized, styrene, α-methylstyrene, p -methylstyrene, or the like may be added, and styrene is most preferable. The weight ratio of the aromatic vinyl monomer in the components of the whole copolymer resin corresponds to 50 to 82% by weight. One or more types of monomers copolymerizable with the aromatic vinyl monomers may be introduced and applied thereto. As the monomer to be introduced, an unsaturated nitrile-based compound such as acrylonitrile or methacrylonitrile is preferable, and 18 to 50 wt% of the components of the entire copolymer is introduced. Further, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be added thereto and copolymerized.

In the rubber-modified SAN copolymer resin (A), the content of the SAN graft copolymer resin (a ₁ ) is 20 to 100% by weight and the content of the SAN copolymer resin (a ₂ ) is 0 to 80% by weight.

(B) polyphenylene ether resin

Since only the rubber-modified SAN copolymer resin is insufficient in flame retardancy and deteriorates rigidity and heat resistance, polyphenylene ether resin is added and used as the base resin. Poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene ) Ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl -1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3) Copolymers of 6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,5-triethyl-1,4-phenyl Ene) ethers. Preferably a copolymer of poly (2,6-dimethyl-1,4-phenylene) ether with poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl -1,4-phenylene) ether is used, more preferably poly (2,6-dimethyl-1,4-phenylene) ether. Although the polymerization degree of polyphenylene ether is not specifically limited, It is preferable that the intrinsic viscosity measured in 25 degreeC chloroform solvent is 0.2-0.8 in consideration of the heat resistance and workability of a resin composition.

(C) SAN (styrene-acrylonitrile) copolymer resin having an acrylonitrile content of 5 to 18 wt%

The SAN copolymer resin is a polymer added to improve compatibility of the rubber-modified SAN copolymer resin and the polyphenylene ether resin. The content of styrene in the components of the SAN copolymer resin is 82 to 95% by weight and the content of acrylonitrile is 5 to 18% by weight. The polymerization method of the SAN copolymer may be prepared by applying emulsification, suspension, bulk polymerization and the like, and a suitable weight average molecular weight is 50,000 to 200,000. Monomers which can be further copolymerized to the styrene-acrylonitrile include methacrylate or phenylmaleimide. Styrene may be replaced with α-methylstyrene or the like for improving heat resistance. The addition amount of the SAN copolymer is added to improve the compatibility of the blend of rubber-modified SAN copolymer resin (A) and polyphenylene ether resin (B) 100 parts by weight of the blend of (A) and (B) It can be applied in the range of 2 to 30 parts by weight.

(D) Carboxy Phosphonic Acid Compounds

In the present invention, a carboxy phosphinic acid compound represented by the following structural formula (1) is used.

Structural Formula 1

In formula (1), R ₁ is hydrogen, a C ₁ -C ₁₂ alkyl group, a C ₆ -C ₁₅ aryl group, or a C ₆ -C ₁₅ aryl group substituted with an alkyl group, and R ₂ is C ₁ -C Or a C ₆ to C ₁₂ aryl group in which an alkylene group of ₁₂ , a cyclic alkylene group, a C _{6 to} C ₁₂ aryl group, or an alkyl group is substituted. 2-carboxy-ethyl-methyl-phosphonic acid, 2-carboxy-ethyl-phenyl-phosphonic acid and 2-carboxy-methyl-phenyl-phosphonic acid are typical examples. These carboxy phosphonic acid compounds may be applied alone or in mixture of two or more.

(E) phosphate ester compound

Phosphoric acid ester that can be used in the present invention is a compound having the following structure and corresponds to the formula (2).

Structural Formula 2

R ₃ , R ₄ and R ₅ in the above formula (2) are each independently hydrogen or an alkyl group of C _{1 to} C ₄ ; X is a C ₆ -C ₂₀ aryl group or an alkyl group substituted C ₆ -C ₂₀ aryl group derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A and bisphenol-S; And m ranges from 0 to 4. Examples of the compound corresponding to Structural Formula (2) include triphenylphosphate, tricresylphosphate, trigyrenylphosphate, tri (2,6-dimethylphenyl) phosphate, and tri (2,4,6-tri when m is 0. Methylphenyl) phosphate, tri (2,4-dibutylbutylphenyl) phosphate, tri (2,6-dibutylbutylphenyl) phosphate, etc., where m is 1, resorcinol bis (diphenyl) phosphate Nolbis (2,6-dimethylphenyl) phosphate, resorcinolbis (2,4-dibutylbutylphenyl) phosphate, hydroquinolbis (2,6-dimethylphenyl) phosphate, hydroquinolbis (2,4-diter Sheryl butylphenyl) phosphate etc. are typical examples. These phosphoric acid ester compounds are applied alone or in mixture of two or more.

In the thermoplastic resin production of the present invention, at least one member selected from the group consisting of polyamide resins, polycarbonate resins, polystyrene resins and rubber-reinforced styrene resins is in the range of 0 to 50 parts by weight based on 100 parts by weight of the base resin of the present invention. Can be used within.

In addition, antidropping agents, impact modifiers, inorganic additives, thermal stabilizers, antioxidants, light stabilizers, pigments, and / or dyes may be added depending on the respective use. The inorganic additives to be added include asbestos, glass fibers, talc, ceramics, sulfates, and the like, which may be used within the range of 0 to 50 parts by weight based on 100 parts by weight of the base resin of the present invention.

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

Example

Preparation and specifications of the base resin, the compatibilizer and the flame retardant used in the examples and comparative examples described in Table 1 are as follows.

(A) Rubber modified SAN copolymer resin (ABS resin)

(a ₁ ) SAN graft copolymer resin

To 50 parts by weight of the butadiene rubber latex solid, 36 parts by weight of grafted monomer styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water were added, and then 1.0 part by weight of potassium oleate and cumene hydroperoxide 0.4 based on the total solids. By weight, 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 reacted while maintaining at 75 ℃ for 5 hours to prepare a graft ABS latex.

0.4 parts by weight of sulfuric acid was added to the prepared graft ABS latex and solidified to prepare a graft copolymer resin (g-ABS) powder.

(a ₂ ) Styrene-containing copolymer resin (AN content 25% SAN copolymer resin)

75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.15 part by weight of azobisisobutyronitrile, 0.4 part by weight of tricalcium phosphate, and 0.2 part by weight of mercaptan-based chain transfer agent were added thereto for 90 minutes. The copolymer resin (SAN) having an acrylonitrile content of 25% by weight was prepared by maintaining the temperature at room temperature to 80 ° C. and maintaining the temperature at this temperature for 180 minutes. It was washed with water, dehydrated and dried to prepare a SAN powder.

(B) polyphenylene ether (PPE) resin

Poly (2,6-dimethyl-1,4-phenylene) ether (trade name P-402) of Asahi Kasei of Japan was used. The particles were in the form of a powder with an average particle diameter of several tens of micrometers.

(C) SAN (styrene-acrylonitrile) copolymer resin (AN content 13% SAN copolymer resin)

Styrene 87 parts by weight, 13 parts by weight of acrylonitrile 120 parts by weight of deionized water, 0.1 part by weight of azobisisobutyronitrile, 1,1'-di (tertiarybutylperoxy) -3,3 ', 5-trimethyl After adding 0.2 parts by weight of cyclohexane, 0.4 parts by weight of tricalcium phosphate, and 0.2 parts by weight of mercaptan-based chain transfer agent, the temperature was raised from 80 ° C. to 90 ° C. for 90 minutes, and then maintained at this temperature for 150 minutes. And 120 minutes was maintained to prepare a copolymer resin (SAN) having an acrylonitrile content of 13%. It was washed with water, dehydrated and dried to prepare a SAN powder.

(D) Carboxy Phosphonic Acid Compounds

2-carboxy-ethyl-phenyl-phosphonic acid having a melting point of 160 to 162 캜 was used.

(E) Aromatic Phosphate Ester Compounds

Triphenyl phosphate having a melting point of 48 ° C. was used.

The materials of (A) to (E) indicated above are added to the contents as shown in Table 1 below, and extruded at a temperature range of 200 to 280 ° C. in a conventional twin screw extruder to prepare pellets.

The prepared pellets were dried at 80 ° C. for 3 hours, and then injected into a 6 Oz injection machine at a molding temperature of 220 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a physical specimen. The prepared specimens were measured for flame retardancy according to UL 94 VB flame retardant regulations.

Example 1 Example 2 Comparative Example (A) ABS resin (a ₁ ) SAN graft copolymer resin 40 40 40 (a ₂ ) SAN copolymer resin 25 25 25 (B) polyphenylene ether resin 35 35 35 (C) SAN copolymer resin 11 11 11 (D) carboxy phosphinic acid 18 5 0 (E) Aromatic Phosphate Ester 0 13 18 Flame retardant degree (1/12 ″) V-0 V-0 V-1

As shown in Table 1, Examples 1 and 2 were applied together with carboxy phosphonic acid and triphenyl phosphate as a flame retardant or carboxy phosphonic acid alone, and in the comparative example, only triphenyl phosphate was applied as a flame retardant. . In addition to the triphenyl phosphate as a flame retardant to the resin when using carboxy phosphinic acid or carboxy phosphinic acid alone it can be seen that the flame retardancy is much improved compared to the case of using triphenyl phosphate alone. The addition of carboxy phosphinic acid to the resin facilitates the formation of char and results in the formation of a harder char coating, resulting in a flame retardancy of UL 94 V-0.

That is, in the present invention, a thermoplastic flame retardant resin composition having improved flame retardancy is prepared by using carboxy phosphinic acid in combination or solely with an aromatic phosphate ester compound as a flame retardant in the resin composition.

The present invention is a thermoplastic resin composition having improved flame retardancy and heat resistance than a conventional resin composition, and it is 5 to 18% by weight as a compatibilizer for preparing a flame retardant resin of a rubber-modified SAN copolymer resin and a polyphenylene ether blend containing no harmful halogen. It has the effect of applying a SAN copolymer resin having an acrylonitrile content of and using a carboxy phosphinic acid and an aromatic phosphate ester compound as a flame retardant to provide a resin composition excellent in flame retardancy.

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 (7)

_{(A) (a 1) 10~60} % 90~40% by weight of the rubber component and the SAN copolymer SAN graft copolymer resin, 20 to 100% by weight consisting of the weight of (a ₂₎ SAN copolymer resin 80~ 40 to 95 parts by weight of a rubber-modified SAN copolymer resin having 0% by weight and having an acrylonitrile content of 18 to 50% by weight, except for the rubber component; (B) 60 to 5 parts by weight of polyphenylene ether resin; (C) 2 to 30 parts by weight of a SAN copolymer resin having an acrylonitrile content of 5 to 18% by weight based on 100 parts by weight of the base resin (A) + (B); (D) 0.5 to 20 parts by weight of the carboxy phosphonic acid compound based on 100 parts by weight of the base resin (A) + (B); And (E) 0-30 weight part of aromatic phosphoric acid ester compound with respect to 100 weight part of basic resins (A) + (B); Thermoplastic flame retardant resin composition, characterized in that consisting of. The thermoplastic flame retardant resin composition according to claim 1, wherein the polyphenylene ether resin (B) is poly (2,6-dimethyl-1,4-phenylene) ether. The halogen-free thermoplastic flame retardant resin composition according to claim 1, wherein the carboxy phosphinic acid compound (C) is a compound characterized by the following structural formula (1): In the above structural formula, R ₁ is hydrogen, a C _{1 to} C ₁₂ alkyl group, a C _{6 to} C ₁₅ aryl group, or a C ₆ to C ₁₅ aryl group substituted with an alkyl group, R ₂ is a C ₁ to C ₁₂ An alkylene group or a cyclic alkylene group, a C ₆ -C ₁₂ aryl group, or a C ₆ -C ₁₂ aryl group substituted with an alkyl group. The flame-retardant thermoplastic resin composition of claim 1, wherein the aromatic phosphate ester compound (E) is a compound characterized by the following structural formula (2), which may be applied alone or in a mixture of two or more: R ₃ , R ₄ , and R ₅ in the above structural formulas are each independently hydrogen, an alkyl group of C _{1 to} C ₄ ; X is a C ₆ -C ₂₀ aryl group substituted with a C ₆ -C ₂₀ aryl group or an alkyl group, and is derived from dialcohols such as resorcinol, hydroquinol, bisphenol-A, bisphenol-S and the like; And m is from 0 to 4. According to claim 1, wherein the thermoplastic resin composition is 0 to 50 parts by weight of one or more selected from the group consisting of polyamide resin, polycarbonate resin, polystyrene resin and rubber-reinforced styrene resin based on 100 parts by weight of the base resin Thermoplastic flame retardant resin composition comprising a. The antidripping agent of claim 1. A thermoplastic flame retardant resin composition further comprising at least one selected from the group consisting of plasticizers, heat stabilizers, antioxidants, light stabilizers, compatibilizers, pigments and / or dyes and inorganic additives. A molded article processed by the resin composition according to any one of claims 1 to 6.