KR100442937B1 - Flame Retardant Thermoplastic Resin Composition - Google Patents

Abstract

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

In formula (I), R ₁ is the same or independently of each other a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group, x is 1 or 2;

In formula (II), R ₂ , R ₃ , R ₅ and R ₆ are each independently C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₄ is C ₆ -C ₃₀ aryl An ylene or alkyl substituted C ₆ -C ₃₀ arylene group, n represents the number of repeat units, and the average value of n is 0.3 to 5; And (E) 0.05 to 5 parts by weight of the fluorinated polyolefin resin with respect to 100 parts by weight of the base 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 resistance and mechanical strength. More specifically, the present invention is composed of polycarbonate resin, rubber modified vinyl graft copolymer, vinyl copolymer, phosphate ester morphide compound, oligomeric phosphate ester compound and fluorinated polyolefin resin, excellent flame resistance and heat resistance And a flame retardant thermoplastic resin composition exhibiting heat resistance and excellent impact resistance, stress cracking resistance, thermal stability and workability.

Background of the Invention

Blends of polycarbonate / vinyl-based 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 retardancy to such a resin composition, a halogen flame retardant and an antimony compound have been used in the past. However, when halogen-based flame retardants are used, the demand for resins that do not contain halogen-based flame retardants has been rapidly expanding recently because of the human hazards of gases generated during combustion. Therefore, it is a trend to manufacture flame-retardant resin using a phosphorus-based flame retardant containing no halogen.

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 5,061,745 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, this resin composition has a problem in that a so-called "juicing" phenomenon occurs in which the flame retardant moves to the surface of the molding during molding.

Oligomeric phosphate ester compounds are also known to be used as flame retardants, and Japanese Patent Laid-Open No. 59-202,240 discloses a process for preparing such compounds. It is also disclosed that the compounds can be used as flame retardants of polyamide or polycarbonate resins. 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 5,672,645 discloses PC / ABS resin compositions consisting 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.

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, of the formula 1 and 2 on the specification R ₁ and R _{When the two} groups are a hydrogen atom, an alkyl group, a cycloalkyl group, an allyl group, a phenyl group or an arylalkyl group, a problem occurs that the hydrolysis resistance of the flame retardant is extremely reduced. In addition, in the case where the R ₁ and R ₂ groups form a morphide group in a cyclic manner, when the structure is the same as the dimorphidephenyl phosphate as in Formula 2 of the patent, when it is added to the resin composition, the flame retardancy of the resin composition The impact strength is drastically lowered and the flame retardant volatilizes, causing the juice to accumulate on the surface of the molded article.

Accordingly, the present inventors solved the conventional problems, and composed of polycarbonate resin, rubber modified vinyl graft copolymer, vinyl copolymer, phosphate ester morphide compound, oligomeric phosphate ester compound, and fluorinated polyolefin resin. It has been developed a flame retardant thermoplastic resin composition excellent in heat resistance and heat and moisture resistance, excellent balance of physical properties such as impact resistance, stress crack resistance, thermal stability and workability.

An object of the present invention is flame retardancy, heat resistance and heat and moisture resistance excellent flame retardance composed of polycarbonate resin, rubber modified vinyl graft copolymer, vinyl copolymer, phosphate ester morphide compound, phosphate ester compound and fluorinated polyolefin resin It is for providing a thermoplastic resin composition.

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

Both 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.

Flame retardant thermoplastic resin composition of the present invention

(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 their 50-95 parts by weight of the mixture with (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 -C _{4 to} 95 parts by weight of a mixture of monomers consisting of 5 to 50 parts by weight of an alkyl or phenyl N-substituted maleimide or mixtures thereof (B-2) butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acryl 5 to 95 parts by weight of a polymer selected from nitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composite or mixtures thereof 1-50 obtained by shunt polymerization 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) 5-95 weight part of monomeric phosphate ester morphide compounds represented by following formula (I), and (D-2) oligomeric phosphate ester type compound represented by following formula (II), or A mixture of 95-5 parts by weight of the mixture, which is 1-30 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C):

In formula (I), R ₁ is the same or independently of each other a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group, x is 1 or 2;

In formula (II), R ₂ , R ₃ , R ₅ and R ₆ are each independently C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₄ is C ₆ -C ₃₀ aryl An ylene or alkyl substituted C ₆ -C ₃₀ arylene group, n represents the number of repeat units, and the average value of n is 0.3 to 5; And

(E) 0.05 to 5 parts by weight of 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 base resin component (A) + (B) + (C). It consists of resin.

Hereinafter, (A) polycarbonate resin which is each component of the flame-retardant thermoplastic resin composition of this invention, (B) rubber modified vinyl type graft copolymer, (C) vinyl type copolymer, (D-1) phosphate ester morphide The compound, (D-2) oligomeric phosphate ester compound, and (E) fluorinated polyolefin resin will be described in detail.

(A) polycarbonate resin

The aromatic polycarbonate resin (A) used in the preparation of the resin composition of 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 -C ₆ cycloalkylidene, -S- or -SO _2- )

Specific examples of the diphenol represented by the 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, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, and the like. 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 preferred, and the aromatic polycarbonate most used industrially is prepared from 2,2-bis- (4-hydroxyphenyl) -propane, also called bisphenol-A.

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 also 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-1.1) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, 50 to 95 parts by weight of C ₁ -C ₈ acrylic acid alkyl esters or mixtures thereof (B-1.2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ 5 to 95 parts by weight of the monomer mixture (B-1) consisting of 5 to 50 parts by weight of acrylic acid alkyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl N-substituted maleimide, or mixtures thereof is selected from 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 rubber composites or these As a mixture of It is obtained by graft polymerization to 5 to 95 parts by weight of the rubbery polymer (B-2) selected from.

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. Ryu. Specific examples of these 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 vinyl graft copolymer (B) include graft copolymers of styrene and acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers in the form of a mixture of butadiene rubber, acrylic rubber, or styrene / butadiene rubber. Can be mentioned.

Other preferable vinyl graft copolymers (B) include those obtained by graft copolymerization of a monomer of (meth) acrylic acid methyl ester to butadiene rubber, acrylic rubber, or styrene / butadiene rubber.

More preferred graft copolymers (B) are ABS graft 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. Is the above-mentioned aromatic vinyl monomer in the presence of a rubbery polymer and is emulsion polymerization or bulk polymerization using a polymerization initiator.

(C) vinyl copolymer

Examples of the vinyl copolymer (C) used in the preparation of the resin composition of the present invention include (C-1) styrene, α-methylstyrene, halogen or alkyl substituted styrene, C ₁ -C ₈ methacrylic acid alkyl esters, and 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 vinyl copolymers obtained by copolymerizing 5 to 50 parts by weight of esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl N-substituted maleimides or mixtures thereof, or mixtures of these copolymers.

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-based 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-based 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 monomer mixtures of methacrylic acid methyl ester monomers and optionally acrylic acid methyl esters. The methacrylic acid methyl ester polymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and a weight average molecular weight of 20,000 to 250,000 is preferably used.

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, preferably, 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 production 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 monomeric phosphate ester morphide compound represented by the following formula (I) or a mixture thereof:

R ₁ in formula (I) is the same or independently of each other a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group, x is 1 or 2.

Preferred R ₁ in the formula (I) is a phenyl group or a naphthyl group or 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 method for preparing a phosphate ester morphide compound such as Formula (I) according to the present invention is not particularly limited. Typically, aromatic alcohol and morpholine having an R ₁ group in phosphorous oxychloride (POCl ₃ ) ) Is prepared by reacting at the same time or sequentially at a temperature of 50 ℃ to 200 ℃. The composite produced by this method may contain about 0 to 20% by weight of triaryl phosphate depending on the reaction process, the composite is used as it is or purified. Catalysts that can be used to prepare phosphate ester morphide compounds such as Formula (I) according to the present invention include aluminum chloride (AlCl ₃ ), magnesium chloride (MgCl ₂ ) or zinc chloride (ZnCl ₂ ) There is a metal chloride, it is also preferable to add a trivalent amine such as triethylamine to remove the hydrogen chloride (HCl) produced by the reaction.

(D-2) Oligomeric Phosphate Ester Compound

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

In formula (II), R ₂ , R ₃ , R ₅ and R ₆ are each independently C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group, and R ₄ is C ₆ -C ₃₀ arylene Or an alkyl substituted C ₆ -C ₃₀ arylene group, n represents the number of repeat units, and the average value of n is 0.3 to 5.

Preferred R ₂ , R ₃ , R ₅ and R ₆ of formula (II) are each a phenyl group or a naphthyl group or methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, Alkyl groups, such as t-amyl, are substituted phenyl groups, and the phenyl group in which a phenyl group, a naphthyl group, or a methyl, ethyl, isopropyl, or t-butyl group was substituted is more preferable.

Preferred R ₄ is resorcinol, hydroquinone or bisphenol-A derivatives.

The compounds of the formula (Ⅱ) used for producing the resin composition of the present invention is C ₆ -C ₃₀ aryl is an alkylene or alkyl substituted C ₆ -C ₃₀ aryl group derived from an oligomer type phosphoric acid ester compound. Preferred C ₆ -C ₃₀ arylene or alkyl substituted C ₆ -C ₃₀ arylene groups are those derived from resorcinol, hydroquinone or bisphenol-A.

In other words, the oligomeric phosphate ester compound (D-2) used as a flame retardant in the preparation of the resin composition of the present invention is an oligomeric aryl derived phosphate ester having an average value of n of 0.3 to 5. In the present invention, a phosphate ester compound having a different value of n may be used alone or in a mixed form, each of which is already mixed when each is prepared in a polymerization process, or a phosphoric acid having a different value of n prepared separately. It is also preferable to use a mixture of ester compounds.

The content of the mixture (D) of the organophosphorus compound used in the preparation of the resin composition of the present invention is 1 to 30 parts by weight based on 100 parts by weight of the base resin component (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 may be prepared using a known polymerization method, for example, a pressure of 7 to 71 kg / cm 2 and a temperature of 0 to 200 ° C., 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 content of the fluorinated polyolefin resin used in the production of the resin composition of the present invention is 0.05 to 5 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C).

In the flame retardant thermoplastic resin composition of the present invention, in order to improve the flame retardancy, in addition to the components described above, generally widely used flame retardants and flame retardant aids such as other organic phosphate ester compounds, halogen-containing organic compounds, cyanate compounds, metal salts, etc. may be additionally used. Can be.

Organic phosphate ester compounds that can be used include monomer type condensed phosphate esters such as triphenyl phosphate, diphenylnaphthyl phosphate and tricresyl phosphate, and the like, and metal salts that can be used as flame retardant aids are commonly known sulfonic acid metal salts and sulfone sulfonic acid metal salts. There is this. 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 this invention can be manufactured by the well-known method of manufacturing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.

The flame retardant thermoplastic resin composition according to the present invention exhibits excellent flame resistance, heat resistance, heat and humidity resistance, and mechanical strength, and has excellent balance of physical properties such as impact resistance, thermal stability, workability, and appearance characteristics, and thus can be used for molding various products. It is particularly suitable for the manufacture of housings of electrical and electronic products, such as computer housings, which 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, (D-1) phosphate ester morphide compound used in the following Examples and Comparative Examples, The specifications of the D-2) oligomer-type phosphate ester compound and (E) fluorinated polyolefin resin are 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 53 parts by weight based on the total amount of monomers, 1.0 parts by weight of potassium oleate, cumene hydroperoxide, an additive necessary for a mixture of 35 parts by weight of styrene, 12 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, solidified 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, 0.17 part by weight of azobisisobutyronitrile, 0.4 part by weight of t-dodecyl mercaptan chain transfer agent and 0.5 part by weight of tricalcium phosphate The suspension was polymerized for 5 hours at 75 ° C. to prepare a SAN copolymer resin. The copolymer was washed with water, dehydrated and dried to obtain a SAN copolymer resin in powder form.

(D-1) Phosphate Ester Morphoxide Compound

Phosphoric acid ester matrix obtained by reacting phosphorus oxychloride with phenol and morpholine, comprising 13% by weight of triphenylphosphate, and 87% by weight of a compound wherein R ₁ is a phenyl group and x is 1 in Formula (I). A mixture of polyd compounds was used.

(D-2) Oligomeric Phosphate Ester Compound

(D-2.1) In formula (II), n is 0, 3.4 wt%, n is 1, 85.4 wt%, and n is 2 or more is included, 11.1 wt%, the average n value is 1.08, R ₂ CR-741S (trade name) from Daihachi, Japan, which is a mixture of bisphenol-A derived oligomeric phosphate esters in which R ₃ , R ₅ and R ₆ are each a phenyl group, was used.

(D-2.1) In formula (II), n is 0, 2.5 wt%, n is 1, 67.2 wt%, n is 2, 21.5 wt% and n is 3 or more, 7.5 wt% is included, CR-733S (trade name) from Daihachi, Japan, which was a mixture of resorcinol-derived oligomeric phosphate esters having an average n value of 1.21 and R ₂ , R ₃ , R _5, and R ₆ each being a phenyl group, was used.

(E) fluorinated polyolefin resin

Dupont, Teflon 7AJ (trade name) was used.

Examples 1-5 and Comparative Examples 1-2

Using the above components, the same resin compositions as those shown in Examples 1 to 5 and Comparative Examples 1 and 2 of Table 1 were prepared, and their physical properties are also shown in Table 1 below.

In Examples 1 to 5, a phosphate ester morphide compound (D-1) and an oligomeric phosphate ester compound (D-2) were used as an organophosphorus compound (D). De compound (D-1) was used, and in Comparative Example 2, only oligomeric phosphate ester compound (D-2) was used.

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

Specimens for flame retardancy and mechanical properties were also prepared using a 10 oz injection machine at 240 ° C. These specimens were measured for 48 hours at 23 ° C. and 50% relative humidity, and then measured physical properties and flame retardancy.

Heat distortion temperature was measured at 18.6 kgf load in accordance with ASTM D648.

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 1.6 mm thick specimen in accordance with UL-94 regulations.

Example Comparative Example One 2 3 4 5 One 2 Furtherance (A) polycarbonate resin 85 85 85 85 85 85 85 (B) Vinyl Graft Copolymer 8 8 8 8 8 8 8 (C) vinyl copolymer 7 7 7 7 7 7 7 (D) organophosphorus compounds (D-1) 9 7 5 3 7 11 - (D-2.1) 2 4 6 8 - - 11 (D-2.2) - - - - 4 - - (E) fluorinated polyolefin resin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Properties UL 94 Flame Retardant (1/16 ") V-0 V-0 V-0 V-0 V-0 V-0 V-1 Heat Deflection Temperature (℃) 95 95 96 95 94 94 95 Izod impact strength (1/8 ", kgcm / cm) Before aging 41 42 41 40 43 38 40 After aging 14 16 18 15 13 11 8

From the results in Table 1 above, the resin composition of the present invention used as a flame retardant by mixing a phosphate ester morphide compound (D-1) and an oligomeric phosphate ester compound (D-2) in an appropriate ratio, each of which is used alone It can be seen that a synergistic effect is exhibited in the heat and humidity resistance without a decrease in flame retardancy and heat resistance as compared with the case.

The present invention is used as a flame retardant by mixing a phosphate ester morphide compound and an oligomeric phosphate ester-based compound to a thermoplastic resin composition having excellent flame resistance, heat resistance and heat and moisture resistance, and excellent impact resistance, stress crack resistance, thermal stability and workability Has the effect of providing.

Claims (6)

(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 their 50-95 parts by weight of the mixture with (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 -C _{4 to} 95 parts by weight of a mixture of monomers consisting of 5 to 50 parts by weight of an alkyl or phenyl N-substituted maleimide or mixtures thereof (B-2) butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acryl 5 to 95 parts by weight of a polymer selected from nitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composite or mixtures thereof 1-50 obtained by shunt polymerization 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) 5-95 weight part of monomeric phosphate ester morphide compounds represented by following formula (I), and (D-2) oligomeric phosphate ester type compound represented by following formula (II), or A mixture of 95-5 parts by weight of the mixture, which is 1-30 parts by weight based on 100 parts by weight of the base resin component (A) + (B) + (C): In formula (I), R ₁ is the same or independently of each other a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group, x is 1 or 2; In formula (II), R ₂ , R ₃ , R ₅ and R ₆ are each independently C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, and R ₄ is C ₆ -C ₃₀ aryl An ylene or alkyl substituted C ₆ -C ₃₀ arylene group, n represents the number of repeat units, and the average value of n is 0.3 to 5; And (E) 0.05 to 5 parts by weight of 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 base resin component (A) + (B) + (C). System resin; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The flame retardant thermoplastic resin composition according to claim 1, wherein R _{1 in} Formula (I) is a phenyl group, a naphthyl group or a phenyl group substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl or t-butyl. A compound according to claim 1, wherein R ₂ , R ₃ , R ₅ and R _{6 in} formula (II) are each a phenyl group, a naphthyl group or a phenyl group substituted with an alkyl group such as methyl, ethyl, isopropyl or t-butyl. Flame retardant thermoplastic resin composition. The flame-retardant thermoplastic resin composition according to claim 1, wherein R ₄ in formula (II) is resorcinol, hydroquinone or bisphenol-A derivative. The flame retardant thermoplastic resin composition according to claim 1, wherein x in the formula (I) is 1. A molded article prepared from the flame retardant thermoplastic resin composition of any one of claims 1 to 5.