KR100442939B1 - Flame Retardant Thermoplastic Resin Composition - Google Patents

Abstract

The flame retardant thermoplastic resin composition of the present invention comprises (A) 45 to 95 parts by weight of a thermoplastic polycarbonate resin; (B) 1 to 50 parts by weight of rubber modified vinyl graft copolymer; (C) 0-50 parts by weight of the vinyl copolymer or a mixture thereof; (D) (D-1) 5 to 95 parts by weight of a phosphate ester morpholide compound represented by the following formula (I) or a mixture thereof and (D-2) a monomeric phosphate ester compound represented by the following formula (II) 95 A mixture of the organophosphorous compound, which is 1-30 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C), as a mixture of -5 parts by weight:

Wherein L is 1 or 2, R ₁ , R ₄ and R ₅ are each independently C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₂ and R ₃ are each independently C ₆ -C ₃₀ arylene or an alkyl substituted C ₆ -C ₃₀ arylene group, x and y each represent the number of corresponding repeating units, and the average value of x + y in the mixture of phosphate ester morpholide compounds is at 0 5;

R ₆ , R ₇ and R ₈ are each independently a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group; And (E) 0.05 to 5 parts by weight of the fluorinated polyolefin resin with respect to 100 parts by weight of the basic resin component (A) + (B) + (C).

Description

Flame Retardant Thermoplastic Resin Composition

Field of invention

The present invention relates to a polycarbonate-based thermoplastic resin composition excellent in flame retardancy, heat-humidity resistance and impact resistance. More specifically, the present invention is composed of a polycarbonate resin, a rubber modified vinyl graft copolymer, a vinyl copolymer, a phosphate ester morphide compound, a phosphate ester compound, and a fluorinated polyolefin resin, and thus excellent flame resistance, heat and moisture resistance, and A flame retardant thermoplastic resin composition having impact resistance and excellent chemical resistance, hydrolysis resistance, stress cracking resistance, thermal stability and workability.

Background of the Invention

Improving the flame retardancy of thermoplastic resins has long been a major goal of resin research and development. Flame retardancy is typically evaluated according to the UL-94 evaluation standard defined by the Underwriters Laboratory. In the evaluation of flame retardancy, when the flame was applied, each specimen burned within 10 seconds, and the total flame out time when the flame was applied twice to five specimens was 50 seconds or less. I can receive it.

Blends of polycarbonate / styrene-containing copolymers are resin mixtures that improve processability while maintaining high notch impact strength and are therefore highly flame retardant and highly flame retardant because they are typically applied to large heat dissipating materials such as computer housings or other office equipment. Mechanical strength must be maintained. In order to impart flame retardance to such a resin composition, a halogen-based flame retardant and an antimony compound have been conventionally used. However, when the halogen flame retardant is used, the demand for a resin that does not contain a halogen flame retardant has been rapidly expanded recently due to the problem of human body harmful gas generated during combustion. Therefore, it is a trend to manufacture flame-retardant resins using a halogen-free (non-halogen-based) phosphorous flame retardant.

As a technique for imparting flame retardancy without using a halogen flame retardant, the most common at present is to use a phosphate ester flame retardant. U.S. Pat. No. 4,692,488 discloses thermoplastics consisting of non-halogen aromatic polycarbonate resins, non-halogen styrene-acrylonitrile copolymers, non-halogen phosphorus compounds, tetrafluoroethylene polymers and small amounts of acrylonitrile-butadiene-styrene graft copolymers. The resin composition is disclosed. U. S. Patent No. 5,061, 745 also discloses a flame retardant resin composition composed of an aromatic polycarbonate resin, an acrylonitrile-butadiene-styrene graft copolymer, a copolymer and a monomeric phosphate ester. However, in such a resin composition, there is a problem in that a so-called "juicing" phenomenon occurs in which the flame retardant moves to the surface of the molding during molding, and there is a problem in that the mechanical properties of the resin composition are greatly reduced when left at a high temperature and high humidity. .

Oligomeric phosphate ester compounds are also known to be used as flame retardants. Japanese Patent Laid-Open No. 59-202,240 discloses a method for preparing such a compound and that the compound can be used as a flame retardant of polyamide or polycarbonate resin. U.S. Patent 5,204,394 discloses flame retardant resin compositions composed of aromatic polycarbonate resins, styrene-containing copolymers or graft copolymers and phosphate ester oligomers. U. S. Patent No. 5,672, 645 also discloses PC / ABS resin compositions composed of aromatic polycarbonate resins, vinyl copolymers, graft copolymers, mixtures of monomeric and oligomeric phosphate esters and fluorinated polyolefins. However, the application of the flame retardant in the form of an oligomeric condensed phosphate ester to a thermoplastic resin has advantages in that less occurrence of juice phenomenon and relatively improved heat resistance compared to the case of using a monomeric phosphate ester. Since the flame retardancy is lowered than when the flame retardant is used, a larger amount of flame retardant must be added to secure an equivalent level of flame retardancy. In addition, there remains a problem that the mechanical properties of the resin composition are greatly reduced when left in a high temperature and high humidity state.

Japanese Patent Application Laid-Open No. 2000-154277 discloses an example but is disclosed that improve the hydrolysis resistance of the phosphoric acid amide-based flame retardant resin composition and flame retardant action by using the thermoplastic resin composition, the flame retardant structural formula 1, R ₁ and R ₂ eseo 2 If the group is a hydrogen atom, an alkyl group, a cycloalkyl group, an allyl group, a phenyl group or an arylalkyl group, there is a problem that the hydrolysis resistance of the flame retardant is extremely reduced. In addition, in the case where the R ₁ and R ₂ groups cyclicly form a morphide group, when the morphoid phenyl phosphate structure (Formula 2) is added to the resin composition, the flame retardancy and impact strength of the resin composition rapidly decreases. In the case where the flame retardant volatilizes and accumulates on the surface of the molded article, the juice phenomenon is severe.

Therefore, the present inventors are composed of a polycarbonate resin, a rubber modified vinyl graft copolymer, a vinyl copolymer, a phosphate ester morphide compound, a phosphate ester compound, and a fluorinated polyolefin resin in order to solve the above problems. It is to develop a flame-retardant thermoplastic resin composition having excellent wettability and impact resistance and excellent physical property balance such as chemical resistance, hydrolysis resistance, stress crack resistance, thermal stability and workability.

An object of the present invention is to provide a flame retardant thermoplastic resin composition excellent in flame retardancy, heat-humidity resistance and impact resistance.

Another object of the present invention is to provide a flame retardant thermoplastic resin composition excellent in flame retardancy, heat-humidity resistance and impact resistance, and excellent in chemical resistance, hydrolysis resistance, stress crack resistance, thermal stability and workability.

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

The flame retardant thermoplastic resin composition of the present invention comprises (A) 45 to 95 parts by weight of a thermoplastic polycarbonate resin; (B) (B-1) (B-1.1) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, or these 50-95 parts by weight of a mixture of (B-1.2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, C _1- 5 to 95 parts by weight of a mixture of monomers consisting of 5 to 50 parts by weight of C ₄ alkyl or phenyl N-substituted maleimide or mixtures thereof (B-2) butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylic 5 to 95 parts by weight of a polymer selected from ronitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites or mixtures thereof 1 to 50 obtained by graft polymerization Rubber-modified vinyl-based graft copolymer negative amount; (C) (C-1) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters or mixtures thereof 50 to 95 weight And (C-2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl N -Substituted 50 to 50 parts by weight of a vinyl copolymer or mixture thereof obtained by copolymerizing 5 to 50 parts by weight of maleimide or a mixture thereof; (D) (D-1) 5 to 95 parts by weight of a phosphate ester morphide compound represented by the following formula (I) or a mixture thereof and (D-2) a monomeric phosphate ester compound represented by the following formula (II): A mixture of the organophosphorous compound, which is 1-30 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C), as a mixture of -5 parts by weight:

Wherein L is 1 or 2, R ₁ , R ₄ and R ₅ are each independently C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₂ and R ₃ are each independently C ₆ -C ₃₀ arylene or an alkyl substituted C ₆ -C ₃₀ arylene group, x and y each represent the number of corresponding repeating units, and the average value of x + y in the mixture of phosphate ester morpholide compounds is at 0 5;

R ₆ , R ₇ and R ₈ are each independently a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group; And (E) a fluorinated polyolefin having an average particle size of 0.05 to 1,000 µm and a density of 1.2 to 2.3 g / cm 3 with respect to 100 parts by weight of the basic resin component (A) + (B) + (C). It is characterized by consisting of a system resin.

Hereinafter, (A) polycarbonate resin, (B) rubber modified vinyl graft copolymer, (C) vinyl copolymer, (D) organophosphorus compound and (E) which are components of the flame retardant thermoplastic resin composition according to the present invention. A fluorinated polyolefin resin is demonstrated in detail.

(A) polycarbonate resin

The aromatic polycarbonate resin (A) used in the present invention can be prepared by reacting diphenols represented by the following formula (III) with phosgene, halogen formate or diester carbonate:

Wherein A is a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C _{5 to} C ₆ cycloalkylidene, -S- or -SO _2- .

Specific examples of the diphenol of formula (III) include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis -(4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane And 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Hydroxyphenyl) -cyclohexane and the like are preferable, and 2,2-bis- (4-hydroxyphenyl) -propane, also called bisphenol-A, is more preferable.

Suitable polycarbonates used in the production of the resin composition of the present invention include those having a weight average molecular weight of 10,000 to 200,000, preferably 15,000 to 80,000.

As the polycarbonate used in the preparation of the resin composition of the present invention, a branched chain may be used, preferably 0.05 to 2 mol% of a tri- or more polyfunctional compound based on the total amount of diphenols used for polymerization, For example, it may be prepared by adding a compound having a trivalent or more phenol group.

Examples of the polycarbonate used in the production of the resin composition of the present invention include homo polycarbonates and copolycarbonates, and may be used in the form of a blend of copolycarbonates and homo polycarbonates.

In addition, the polycarbonate used in the preparation of the resin composition of the present invention may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerizing in the presence of an ester precursor, such as a bifunctional carboxylic acid. .

(B) Rubber modified vinyl graft copolymer

The vinyl graft copolymer (B) used in the preparation of the resin composition of the present invention is (B-1) (B-1.1) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacryl 50 to 95 parts by weight of acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, or mixtures thereof, and (B-1.2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters 5 to 95 parts by weight of a monomer mixture consisting of 5 to 50 parts by weight of C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl N-substituted maleimide or mixtures thereof (B-2) Butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, terpolymer (EPDM) of ethylene-propylene-diene, polyorganosiloxane / polyalkyl (meth) acrylate One or a mixture of rubber composites 5 to 95 parts by weight of a polymer selected from water were obtained sum of the graft.

The C ₁ -C ₈ methacrylic acid alkyl esters or C ₁ -C ₈ acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms as alkyl esters of methacrylic acid or acrylic acid, respectively. to be. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester.

Preferred examples of the rubber-modified vinyl-based graft copolymer (B) of the present invention are grafted in the form of a mixture of styrene and acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers in butadiene rubber, acrylic rubber or styrene / butadiene rubber. The thing copolymerized by transcript is mentioned.

Another preferred rubber-modified vinyl-based graft copolymer (B) is one obtained by graft copolymerization of a monomer of (meth) acrylic acid methyl ester to butadiene rubber, acrylic rubber, or styrene / butadiene rubber. More preferred are ABS graft copolymers or MBS copolymers.

It is preferable to use the particle diameter of the said rubber (B-2) that is 0.05-4 micrometers in order to improve impact strength and the surface characteristic of a molded object.

The method for preparing the graft copolymer is well known to those skilled in the art, and any one of emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization may be used. In the presence of a rubbery polymer, the above-mentioned aromatic vinyl monomer is added to emulsion polymerization or bulk polymerization using a polymerization initiator.

(C) vinyl copolymer

The vinyl copolymer (C) used in the preparation of the resin composition of the present invention is (C-1) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ 50 to 95 parts by weight of -C ₈ acrylic acid alkyl esters or mixtures thereof, and (C-2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ alkyl acrylate And 0 to 50 parts by weight of a vinyl copolymer obtained by copolymerizing 5 to 50 parts by weight of esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl N-substituted maleimide or mixtures thereof.

The C ₁ -C ₈ methacrylic acid alkyl esters or C ₁ -C ₈ acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms as alkyl esters of methacrylic acid or acrylic acid, respectively. to be. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester.

The thermoplastic vinyl copolymer (C) used in the preparation of the resin composition of the present invention can be produced as a by-product in the preparation of the graft copolymer (B), in particular by grafting an excess monomer mixture to a small amount of rubbery polymer. It is more likely to occur in the case of excessive use of the chain transfer agent or the chain transfer agent used as a molecular weight control agent. The content of the vinyl copolymer (C) used in the preparation of the resin composition of the present invention is not shown including the by-product of the graft copolymer (B).

Preferred vinyl copolymers (C) are monomer mixtures of styrene and acrylonitrile and optionally methacrylic acid methyl ester, monomer mixtures or styrene of α-methylstyrene and acrylonitrile and optionally methacrylic acid methyl ester, α- And those prepared from monomer mixtures of methyl styrene and acrylonitrile and optionally methacrylic acid methyl ester. The styrene / acrylonitrile copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and it is preferable to use a weight average molecular weight of 15,000 to 200,000.

Other preferred vinyl copolymers (C) include those prepared from a monomer mixture of methacrylic acid methyl ester monomers and optionally acrylic acid methyl esters. The methacrylic acid methyl ester polymer as the component (C) may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization, and it is preferable to use those having a weight average molecular weight of 20,000 to 250,000.

Another preferred vinyl copolymer (C) is a copolymer of styrene and maleic anhydride, which can be produced using a continuous block polymerization method and a solution polymerization method. The composition ratio of the two monomer components can be varied in a wide range, it is preferable that the content of maleic anhydride is 5 to 50% by weight. The molecular weight of the styrene / maleic anhydride copolymer may also be used in a wide range, but it is preferable to use those having a weight average molecular weight of 20,000 to 200,000 and intrinsic viscosity of 0.3 to 0.9.

The styrene monomers used in the preparation of the vinyl copolymer (C) used in the preparation of the resin composition of the present invention are other substituted vinyls such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and α-methylstyrene. It can be used instead of the monomer.

The vinyl copolymer (C) used in the preparation of the resin composition of the present invention is used alone or in a mixture of two or more thereof.

(D) Organophosphorus Compound

(D-1) Phosphate Ester Morphoxide Compound

The phosphate ester morphide compound used in the preparation of the resin composition of the present invention is a phosphate ester morphide compound represented by the following formula (I) or a mixture thereof:

Wherein L is 1 or 2, R ₁ , R ₄ and R ₅ are each independently C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₂ and R ₃ are each independently C ₆ -C ₃₀ arylene or an alkyl substituted C ₆ -C ₃₀ arylene group, x and y each represent the number of corresponding repeating units, and the average value of x + y in the mixture of phosphate ester morpholide compounds is at 0 5

Preferred R ₁ , R ₄ and R ₅ are each a phenyl group or a naphthyl group or each substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, etc. It is more preferable that it is a phenyl group and a double phenyl group, a naphthyl group, or the methyl, ethyl, isopropyl, or t-butyl group substituted.

Preferred R ₂ and R ₃ are each derived from resorcinol, hydroquinone or bisphenol-A.

The phosphate ester morpholide compound of the formula (I) is a morpholine having an aromatic alcohol having R ₁ , R ₄ and R ₅ groups in phosphorus oxychloride (POCl ₃ ) and morpholine in the presence of a suitable catalyst. Reaction at temperature to obtain aryl morpholino chlorophosphate, and can be prepared by reacting the aryl morpholino chlorophosphate and hydroxy aryl compound having R ₂ and R ₃ groups at a temperature of 70 ~ 220 ℃ using a suitable catalyst have. Or alternatively, first reacting the phosphorus oxychloride with a hydroxy alkyl compound having R ₂ and R ₃ groups, and then sequentially reacting an aromatic alcohol having R ₁ , R ₄ and R ₅ groups with morphine, or It is also possible to react the compounds simultaneously. At this time, a solution polymerization method or a melt polymerization method can be used as a polymerization method.

Catalysts usable for preparing the phosphate ester morphide compound of Formula (I) include metal chlorides such as aluminum chloride (AlCl ₃ ), magnesium chloride (MgCl ₂ ) or zinc chloride (ZnCl ₂ ). It is also preferable to add a trivalent amine such as triethylamine to remove hydrogen chloride (HCl) generated by.

Phosphoric acid ester morphide compound prepared by the above method, x and y values in the case of excessive reaction of morpholine with aromatic alcohol having R ₁ , R ₄ and R ₅ groups in phosphorus oxychloride (POCl ₃ ) Only a monophosphate ester morphide compound of which all are zero may be prepared, and the reaction process may be adjusted to adjust the amount of the compound having both zero values of x and y. In addition, the produced composite can be used as it is or by refine | purifying as a compound.

(D-2) Phosphate Ester Compound

The phosphate ester compound used in the preparation of the resin composition of the present invention is a monomeric phosphate ester compound represented by the following formula (II) or a mixture thereof:

Wherein R ₆ , R ₇ and R ₈ are each independently C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl groups.

Preferred R ₆ , R ₇ and R ₈ are each a phenyl group or a naphthyl group or each substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, etc. It is a phenyl group, and a phenyl group in which a double phenyl group, a naphthyl group, or a methyl, ethyl, isopropyl, or t-butyl group was substituted is more preferable.

The organophosphorus compound (D) used as a flame retardant in the present invention is a mixture of 5 to 95 parts by weight of the phosphate ester morphide compound (D-1) and 95 to 5 parts by weight of the phosphate ester compound (D-2), It is used in the amount of 1-30 weight part with respect to 100 weight part of resin components (A) + (B) + (C).

(E) fluorinated polyolefin resin

The fluorinated polyolefin resin (E) used in the preparation of the flame retardant thermoplastic resin composition of the present invention is a conventionally available resin, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer And tetrafluoroethylene / hexafluoropropylene copolymers and ethylene / tetrafluoroethylene copolymers. These may be used independently from each other, and two or more different types may be used together.

The fluorinated resin used in the preparation of the resin composition of the present invention can be prepared using a known polymerization method, for example, a pressure of 7 to 71 kg / ㎠ and a temperature of 0 to 200 ℃, preferably 20 to 100 It can be prepared in an aqueous medium containing free radical forming catalysts such as sodium, potassium or ammonium peroxydisulfate at conditions of < RTI ID = 0.0 >

The fluorinated polyolefin resin may be used in an emulsion state or a powder state. When the fluorinated polyolefin-based resin in the emulsion state is used, the dispersibility in the entire resin composition is good, but there is a disadvantage in that the manufacturing process is complicated. Therefore, even if it is powder state, if it can disperse | distribute suitably in the whole resin composition and can form a fibrous network, it is preferable to use it in powder state.

Fluorinated polyolefin-based resins which can be preferably used in the preparation of the resin composition of the present invention include polytetrafluoroethylene having a particle size of 0.05 to 1,000 µm and specific gravity of 1.2 to 2.3 g / cm 3. The fluorinated polyolefin resin (E) is used in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C).

In order to improve the flame retardancy, the flame retardant thermoplastic resin composition of the present invention may be added with other widely used flame retardants and flame retardant aids such as other organic phosphate ester compounds, halogen-containing organic compounds, cyanurate compounds, metal salts, and the like, in addition to the above components.

Organic phosphate ester compounds that can be used include oligomeric condensed phosphate esters derived from dihydric alcohols such as resorcinol, hydroquinone and bisphenol-A, and the metal salts usable as flame retardant aids are commonly known sulfonic acid metal salts and sulfone sulfonic acid metal salts. Etc. These may be used independently from each other, and two or more different types may be used together.

In addition to the above components, the flame retardant thermoplastic resin composition of the present invention may include general additives such as lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, inorganic additive pigments or dyes, and the like. Can be used in the range of 0 to 60 parts by weight, preferably 0.5 to 40 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C).

The resin composition of the present invention can be prepared by a known method, for example, the components and other additives of the present invention can be mixed at the same time and then melt-extruded in an extruder and prepared in pellet form.

The resin composition of the present invention can be used for molding a variety of products, and is particularly suitable for the production of housings of electrical and electronic products such as computer housings that require flame retardancy and high impact resistance while being injected at high temperatures.

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

(A) polycarbonate resin, (B) rubber modified vinyl graft copolymer, (C) vinyl copolymer resin, (D) organophosphorus compound and (E) fluorination used in the following Examples and Comparative Examples The specification of polyolefin resin is as follows.

(A) polycarbonate resin

A polycarbonate of bisphenol-A type having a weight average molecular weight (Mw) of 25,000 was used.

(B) Rubber modified vinyl graft copolymer

Butadiene rubber latex was added so that the butadiene content was 50 parts by weight based on the total amount of the monomers, 1.0 parts by weight of potassium oleate, cumene hydroperoxide, which is an additive necessary for a mixture of 36 parts by weight of styrene, 14 parts by weight of acrylonitrile and 150 parts by weight of deionized water. 0.4 parts by weight, 0.3 parts by weight of t-dodecyl mercaptan chain transfer agent was added to the reaction while maintaining at 75 ℃ for 5 hours to prepare an ABS graft latex. A 1% sulfuric acid solution was added to the resulting polymer latex, coagulated and dried to prepare a graft copolymer resin in a powder state.

(C) vinyl copolymer resin

71 parts by weight of styrene, 29 parts by weight of acrylonitrile and 120 parts by weight of deionized water, 0.2 part by weight of azobisisobutyronitrile, 0.3 part by weight of t-dodecyl mercaptan chain transfer agent and 0.5 part by weight of tricalcium phosphate SAN copolymer resin was prepared by addition and suspension polymerization. The copolymer was washed with water, dehydrated and dried to obtain a SAN copolymer resin in powder form.

(D) Organophosphorus Compound

(D-1) Phosphate Ester Morphoxide Compound

(D-1a) Oligomeric Phosphate Ester Morphoxide Compound

Obtained by reacting bisphenol-A with phenyl morpholino chlorophosphate, in which R ₁ , R ₄ and R ₅ are all phenyl groups, R ₂ and R ₃ are all bisphenol-A derivatives, 3.1 wt% of a phosphate ester morpholide compound of which all y is 0 and l is 1, 84.7 wt% of a compound of which l is 1 and the value of x + y is 1, and 1 is 1 and that of x + y is 2 12.2% by weight of the above compound was used.

(D-1b) Monomer Phosphoric Acid Ester Morphoxide Compound

It was obtained by reacting phosphorus oxychloride with phenol and morpholine, containing 9% by weight of triphenylphosphate, wherein R ₁ , R ₄ and R ₅ in the formula (I) are all phenyl groups, 1 is 1 and x and 88 wt% of compounds having a value of 0 for all of y, 2 of l, and 3 wt% of a compound having a value of 0 of both x and y were used.

(D-2) Monomer Phosphoric Acid Ester Compound

In formula (II), triphenyl phosphate (TPP) of Daihachi, Japan, where R ₆ , R ₇ and R ₈ are all phenyl groups, was used.

(E) fluorinated polyolefin resin

DuPont Teflon 7AJ (trade name) was used.

Examples 1-5 and Comparative Examples 1-2

Using the above-mentioned components was prepared a resin composition such as the composition shown in Table 1, their physical properties are also shown in Table 1.

Examples 1 to 5 were used by mixing a phosphate ester morphide compound (D-1) and a monomeric phosphate ester compound (D-2) with an organophosphorus compound (D). In Example 5, a phosphate ester morphide was used. As the compound (D-1), an oligomeric phosphate ester morphide compound (D-1a) and a monomeric phosphate ester morphide compound (D-1b) were mixed and used.

In Comparative Example 1, only the phosphate ester morphide compound (D-1) was used as the organophosphorus compound (D), and in Comparative Example 2, only the monomeric phosphate ester compound (D-2) was used.

Antioxidant and heat stabilizer were added to each component, mixed in a conventional mixer, extruded using a twin screw extruder having L / D = 35 and Φ = 45 mm, and cooled in water to prepare pellets. The pellets were dried at 80 ° C. for at least 5 hours before injection molding.

Specimens for evaluating the gate impact resistance were prepared by a residence time of 50 × 200 × 3 (mm) in a pin-point gate mold at an injection temperature of 240 ° C. using a 10 oz injection machine. Specimens for flame retardancy and mechanical properties were also prepared using a 10 oz injection machine at 240 ° C. The specimens were left at 23 ° C. and 50% relative humidity for 48 hours to measure physical properties and flame retardancy.

Gate impact resistance was evaluated by observing the fracture state that occurs when the round bottom (R = 5 mm) rod-shaped weight (weight 1 kg) falls freely into the pin point gate of the specimen at a height of 50 cm. At this time, the number of specimens showing brittle fracture when the ten specimens were evaluated was measured.

Heat resistance was measured for the change in Izod impact strength after aging for 72 hours at 80 ℃ and 90% relative humidity.

Flame retardancy was evaluated using a 2.1 mm thick specimen in accordance with UL-94.

Example Comparative Example One 2 3 4 5 One 2 Furtherance (A) polycarbonate resin 75 75 75 75 75 75 75 (B) Vinyl Graft Copolymer 11 11 11 11 11 11 11 (C) vinyl copolymer 14 14 14 14 14 14 14 (D) organophosphorus compounds D-1a 9 7 5 3 3 12 - D-1b - - - - 3 - - D-2 3 5 7 9 6 - 12 (E) fluorinated polyolefin resin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Properties UL 94 flame retardant (2.1㎜) V-0 V-0 V-0 V-0 V-0 V-1 V-0 Gate Impact Resistance (Fragile Fractures / 10 Specimen) 1 min residence time 0 0 0 0 0 3 0 2 min residence time 6 5 5 4 5 10 5 Izod impact strength (1/8 ", kgcm / cm) Before aging 44 42 40 39 42 37 45 After aging 16 16 14 11 12 10 3

From the results of Table 1 above, when the resin composition of the present invention used as a flame retardant by mixing the phosphate ester morphide compound (D-1) and the phosphate ester compound (D-2) in an appropriate ratio, each of them alone In contrast, it can be seen that while maintaining flame retardancy, there is a synergistic effect in heat resistance and gate impact strength.

The present invention is a flame retardant by mixing a phosphate ester morphide compound and a phosphate ester compound as a flame retardant, excellent in flame resistance, heat and moisture resistance and impact resistance, while also excellent in chemical resistance, hydrolysis resistance, stress crack resistance, thermal stability and workability It has the effect of providing a thermoplastic resin composition.

Claims (5)

(A) 45 to 95 parts by weight of a thermoplastic polycarbonate resin; (B) (B-1) (B-1.1) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, or these 50-95 parts by weight of a mixture of (B-1.2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, C _1- 5 to 95 parts by weight of a mixture of monomers consisting of 5 to 50 parts by weight of C ₄ alkyl or phenyl N-substituted maleimide or mixtures thereof (B-2) butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylic 5 to 95 parts by weight of a polymer selected from ronitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composites or mixtures thereof 1 to 50 obtained by graft polymerization Rubber-modified vinyl-based graft copolymer negative amount; (C) (C-1) 50 to 95 weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters or mixtures thereof And (C-2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid alkyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl N -Substituted 50 to 50 parts by weight of a vinyl copolymer or mixture thereof obtained by copolymerizing 5 to 50 parts by weight of maleimide or a mixture thereof; (D) (D-1) 5 to 95 parts by weight of a phosphate ester morpholide compound represented by the following formula (I) or a mixture thereof and (D-2) a monomeric phosphate ester compound represented by the following formula (II) 95 A mixture of the organophosphorous compound, which is 1-30 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C), as a mixture of -5 parts by weight: Wherein L is 1 or 2, R ₁ , R ₄ and R ₅ are each independently C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₂ and R ₃ are each independently C ₆ -C ₃₀ arylene or an alkyl substituted C ₆ -C ₃₀ arylene group, x and y each represent the number of corresponding repeating units, and the average value of x + y in the mixture of phosphate ester morpholide compounds is at 0 5; R ₆ , R ₇ and R ₈ are each independently a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group; And 0.05 to 5 parts by weight of the fluorinated polyolefin resin based on 100 parts by weight of the base resin component (A) + (B) + (C); Flame-retardant thermoplastic resin composition, characterized in that consisting of. The R ₁ , R ₄ and R ₅ of the phosphate ester morphide compound (D-1) are each substituted with a phenyl group, a naphthyl group or an alkyl group such as methyl, ethyl, isopropyl or t-butyl. A flame retardant thermoplastic resin composition, characterized in that it is a phenyl group. The flame retardant thermoplastic resin composition according to claim 1, wherein R ₂ and R ₃ of the phosphate ester morphide compound (D-1) are resorcinol, hydroquinone or bisphenol-A derivatives, respectively. The phenyl group according to claim 1, wherein R ₆ , R ₇ and R ₈ of the monomeric phosphate ester compound (D-2) are each substituted with a phenyl group, a naphthyl group or an alkyl group such as methyl, ethyl, isopropyl or t-butyl. Flame retardant thermoplastic resin composition characterized in that. Molded article prepared from the flame-retardant thermoplastic resin composition of any one of claims 1 to 4.