KR20030065923A - Flame Retardant Thermoplastic Resin Composition - Google Patents

Abstract

PURPOSE: Provided is a fire retardant, thermoplastic resin composition which does not exhibit a juicing phenomenon, and simultaneously has excellent fire retardancy, heat resistance, impact resistance, heat stability, workability, and appearance. CONSTITUTION: The composition comprises (A) 45-95 parts by weight of polycarbonate resin; (B) 1-50 parts by weight of rubber-modified vinyl graft copolymer; (C) 0-50 parts by weight of vinyl copolymer; (D) 1-30 parts by weight(based on the sum 100 parts by weight of the basic resin(A)+(B)+(C)) of mixture of organophosphorus compounds consisting of (D-1) 5-95 parts by weight of monomeric ester phosphate compound represented by formula I or a mixture thereof and (D-2) 5-95 parts by weight of ester phosphate morpholide compound represented by formula II or mixture thereof(wherein each of R1 and R2 is independently hydrogen atom, or an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, x is an integer of 1-3, l is 1 or 2, each of R3, R6 and R7 is independently C6-C20 aryl or alkyl-substituted C6-C20 aryl group, each of R4 and R5 is C6-C30 arylene or alkyl substituted with C6-C30 arylene group, m and n represent a number of corresponding repeating unit respectively, an average value of m+n is 0-5 in a mixture of ester phosphate morpholide compounds); and (E) 0.05-5 parts by weight (based on the sum 100 parts by weight of the basic resin(A)+(B)+(C)) of fluorinated polyolefin resin having an average particle size of 0.05-1,000 micrometer and a density of 1.2-2.3 g/cm¬3.

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 a polycarbonate resin, a rubber modified vinyl graft copolymer, a vinyl copolymer, a specific monomeric phosphate ester compound, a phosphate ester morphide compound, and a fluorinated polyolefin resin to exhibit a juice phenomenon. The present invention relates to a flame retardant thermoplastic resin composition excellent in flame retardancy, heat and humidity resistance, heat resistance, impact resistance, heat stability, workability and appearance characteristics.

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 expanded recently due to the problem of human health 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. Patent Nos. 4,692,488 and 5,061,745 disclose flame retardant resin compositions consisting of aromatic polycarbonate resins, acrylonitrile-butadiene-styrene graft copolymers, copolymers and monomeric phosphate esters. However, the resin composition using such a monomeric phosphate ester compound as a flame retardant has a problem that the heat resistance greatly decreases, and a so-called "juicing" phenomenon occurs in which the flame retardant volatilizes during molding and deposits on the surface of the 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 this compound can be used as a flame retardant for 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. 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.

U.S. Patent No. 5,672,645 discloses a PC / ABS resin composition wherein a mixture of a monomeric phosphate ester compound and an oligomeric phosphate ester compound and a fluorinated polyolefin are applied to a composition consisting of an aromatic polycarbonate resin, a vinyl copolymer and a graft copolymer. have. In this case, since a certain amount of monomeric phosphate ester flame retardants such as triphenyl phosphate is present in a predetermined amount or more, the juice phenomenon cannot be completely prevented.

Japanese Patent Application Laid-Open No. 2000-154277 In an example in which call improve the hydrolysis resistance of the working performance of the flame retardant resin composition using phosphoric acid amide flame retardants in thermoplastic resin composition, but is disclosed herein of formula 1 and 2 on the 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, if the structure is the same as that of the dimorphidephenyl phosphate of the structural formula 2, the flame retardancy and the impact strength of the resin composition are added to the resin composition. Is sharply lowered, the flame retardant is volatilized and the juice phenomenon that accumulates on the surface of the molded article is severe.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched and solved the said problem, and, as a result, a polycarbonate resin, a rubber modified vinyl graft copolymer, a vinyl copolymer, a specific monomeric phosphate ester compound, a phosphate ester morphide compound, and a fluorinated polyolefin type It has been developed a flame-retardant resin composition composed of a resin, excellent in the balance of physical properties such as flame resistance, heat and humidity resistance, heat resistance, impact resistance, thermal stability, workability and appearance characteristics without the appearance of juice phenomenon.

An object of the present invention is composed of a polycarbonate resin, a rubber modified vinyl graft copolymer, a vinyl copolymer, a specific monomeric phosphate ester compound, a phosphate ester morphide compound and a fluorinated polyolefin resin, so that no juice phenomenon occurs. It is to provide a flame retardant thermoplastic resin composition.

Another object of the present invention is to provide a flame-retardant thermoplastic resin composition excellent in flame retardancy, heat-humidity resistance, heat resistance, impact resistance, thermal stability, workability and appearance characteristics while not exhibiting a juice phenomenon.

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

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 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 complex or mixtures thereof 1 to 50 obtained by graft 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 methyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl N -Substituted 50 to 50 parts by weight of a vinyl copolymer obtained by copolymerizing 5 to 50 parts by weight of a maleimide or a mixture thereof, or a mixture thereof,

(D) (D-1) 5 to 95 parts by weight of a monomeric phosphate ester compound represented by the following general formula (I) or a mixture thereof, and

(In formula (I), R ₁ and R ₂ are each independently a hydrogen atom or methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, etc. Alkyl group, x is an integer of 1-3.

(D-2) 5 to 95 parts by weight of a phosphate ester morpholide compound represented by the following general formula (II) or a mixture thereof

(In the formula (II), l is 1 or 2, R ₃ , R ₆ and R ₇ are each independently a C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, R ₄ and R ₅ Are each independently a C ₆ -C ₃₀ arylene or an alkyl substituted C ₆ -C ₃₀ arylene group, m and n each represent the number of the corresponding repeating unit, and m + n in the mixture of phosphate ester morphide compounds The average value is 0 to 5.)

A mixture of organophosphorus compounds having a content of (D) in an amount of 1 to 30 parts by weight based on 100 parts by weight of the component (A) + (B) + (C), and

(E) Fluorinated polyolefins having an average particle size of 0.05 to 1,000 µm and a density of 1.2 to 2.3 g / cm ³ based on 100 parts by weight of the component (A) + (B) + (C) It is characterized by consisting 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 compound, ( D-2) A phosphate ester morphide type compound and (E) fluorinated polyolefin type resin are demonstrated in detail.

(A) polycarbonate resin

The aromatic polycarbonate resin, which is the component (A) used in the preparation of the resin composition of the present invention, can be prepared by reacting diphenols represented by the following general formula (III) with phosgene, halogen formate or carbonic acid diester:

Wherein A represents 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 the general 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, and the preferred and most commonly used aromatic polycarbonates are 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 production of the resin composition of the present invention may be partially or entirely replaced by an aromatic polyester-carbonate resin obtained by polymerization 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 to} 95 parts by weight of a 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, 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 composite Or mixtures thereof Since it is obtained by graft-polymerization to the weight parts of the selected rubber-like polymer (B-2) 5~95.

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 those obtained by graft copolymerization of butadiene rubber, acrylic rubber, or styrene / butadiene rubber in the form of a mixture of styrene and acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers. Can be.

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, and a preferred manufacturing method For example, the above-mentioned aromatic vinyl monomer is introduced in the presence of a rubbery polymer, followed by 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 includes (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 vinyl copolymers obtained by copolymerizing 5 to 50 parts by weight of esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl nucleosubstituted maleimide or mixtures thereof, or mixtures of these copolymers.

The C ₁ -C ₈ methacrylic acid alkyl esters or C ₁ -C ₈ methacrylic acid alkyl esters are alkyl esters of methacrylic acid or acrylic acid, respectively, from monohydryl alcohols containing 1 to 8 carbon atoms. Obtained esters. 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.

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), and in particular a small amount of rubbery polymer is grafted with an excess monomer mixture. It is more likely to occur in the case of the use of an excessive amount of 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 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 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 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 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 described above is used alone or in a mixture of two or more thereof.

(D) Organophosphorus Compound

(D-1) Monomer Phosphoric Acid Ester Compound

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

In formula (I), R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl and t-amyl X is an integer of 1-3.

In the above formula, R ₁ and R ₂ are each preferably a hydrogen atom or a methyl, ethyl, isopropyl or t-butyl group, and X is preferably 1 or 2.

Method for producing a phosphate ester compound, such as the structural formula (I) according to the present invention is not particularly limited, and typically an aromatic alcohol and a R ₂ having a naphthyl group substituted with a R ₁ group in phosphorous oxychloride (POCl ₃ ) It is produced by reacting an aromatic alcohol having a substituted phenyl group at the same time or sequentially at a temperature of 50 to 200 ° C. The composite prepared by this method may contain about 0-10% by weight of triaryl phosphate depending on the reaction process, and the composite is used as it is or in purified form. Catalysts that can be used to prepare monomeric phosphate ester compounds such as Structural Formula (I) according to the present invention include chlorides such as aluminum chloride (AlCl ₃ ), magnesium chloride (MgCl ₂ ) or zinc chloride (ZnCl ₂ ). There is a metal.

(D-2) 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 general formula (II) or a mixture thereof:

In Formula (II), l is 1 or 2, R ₃ , R ₆ and R ₇ are each independently a C ₆ -C ₂₀ aryl or alkyl substituted C ₆ -C ₂₀ aryl group, and R ₄ and R ₅ are Each independently is a C ₆ -C ₃₀ arylene or alkyl substituted C ₆ -C ₃₀ arylene group, m and n each represent the number of corresponding repeating units, and the mean value of m + n in the mixture of phosphate ester morpholide compounds Is 0 to 5.

Preferred R ₃ , R ₆ and R ₇ are phenyl or naphthyl groups or substituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl and the like 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.

Preferred R ₄ and R ₅ are those derived from resorcinol, hydroquinone or bisphenol-A.

Phosphoric acid ester morpholide compounds such as the above formula (II) according to the present invention firstly form an aromatic alcohol and morpholine having R ₃ , R ₆ and R ₇ groups in phosphorus oxychloride (POCl ₃ ) in the presence of a suitable catalyst. Reaction at a temperature of 50 to 200 ° C. to obtain an aryl morpholino chlorophosphate, and the hydroxy morpholino chlorophosphate and the dihydroxy arylene compound having R ₄ and R ₅ groups were reacted with an appropriate catalyst at 70 to 220 ° C. It can be prepared by reacting at a temperature. Or alternatively, first reacting the phosphorus oxychloride with the dihydroxy arylene compound having the R ₄ and R ₅ groups, followed by the sequential reaction of the morpholine with the aromatic alcohol having the R ₃ , R ₆ and R ₇ groups, or It is also possible to react the above compounds at the same time. At this time, a solution polymerization method or a melt polymerization method can be used as a polymerization method.

As a catalyst that can be used to prepare a phosphate ester morphide compound such as the above formula (II) according to the present invention, such as aluminum chloride (AlCl ₃ ), magnesium chloride (MgCl ₂ ), zinc chloride (ZnCl ₂ ) There is a metal chloride, it is also preferred to add a trivalent amine such as triethylamine to remove the hydrogen chloride (HCl) produced by the reaction.

Phosphoric acid ester morphide compounds prepared by the above method, the value of m and n when reacting excessively with morpholine aromatic alcohol having R ₃ , R ₆ and R ₇ groups to 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 control the amount of the compound having both zero values of m and n. In addition, the produced composite can be used as it is or as a purified compound.

(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 of 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 / cm ² and a temperature of 0 to 200 ℃, preferably 20 to It can be prepared in an aqueous medium containing a free radical forming catalyst such as sodium, potassium or ammonium peroxydisulfate at 100 ° C.

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 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 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 order to improve the flame retardancy, the flame retardant thermoplastic resin composition of the present invention, in addition to the components described above, may be used in addition to the flame retardants and flame retardant aids that are generally widely commercialized, such as other organic phosphate ester compounds, halogen-containing organic compounds, cyanate compounds, and metal salts. Can be. 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 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 composition of the present invention can be used for molding a variety of products, and is particularly suitable for the manufacture 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 present invention will be further illustrated by the following examples, which are only described for the purpose of illustrating the present invention and are not intended to limit the protection scope of the present invention.

Example

(A) polycarbonate resin

A polycarbonate of bisphenol-A 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 58 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 31 parts by weight of styrene, 11 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, 0.17 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) Mixture of Monomer Phosphate Ester Compounds

A compound obtained by reacting phosphorus oxychloride with phenol and 2-naphthol, containing 2.5% by weight of triphenylphosphate, wherein R ₁ and R ₂ are both hydrogen atoms and x is 1 in General Formula (I). A mixture of 88% by weight, a phosphate ester compound containing 9% by weight of a compound in which both R ₁ and R ₂ are hydrogen atoms and x is 2 was used.

(D-2) Phosphate Ester Morphoxide Compound

(D-2.1) Phosphorus oxychloride was obtained by reacting phenol and morpholine, containing 9% by weight of triphenylphosphate, and in the general formula (II), R ₃ , R ₆ and R ₇ are all phenyl groups. 88 wt% of a compound in which l is 1 and both m and n are 0, and ₃ wt% of a compound in which R ₃ , R ₆ and R ₇ are all phenyl groups, l is 2 and both m and n are 0 Of the prepared monomeric phosphate ester morphide compounds were used.

(D-2.2) In the general formula (I), R ₃ , R ₆ and R ₇ are all phenyl groups and R ₄ and R ₅ are all bisphenol-A derivatives, wherein m and n are both 0 and l This 1 phosphate ester morpholide compound comprises 3.1 wt%, 1 is 1, m + n is 1, and 84.7 wt% is 1, and 1 is 1, and m + n is 2 or more, and 12.2 wt% is included. Of the prepared oligomeric phosphate ester morphide compounds were used.

(E) fluorinated polyolefin resin

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

Examples 1-5

Each component of the composition shown in Table 1, 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 the extrudate was pelleted. The prepared pellets were dried at 80 ° C. for at least 5 hours before injection molding. Specimens for physical property measurement and flame retardancy evaluation at an injection temperature of 240 ° C. were prepared using a 10 oz injection machine. After the specimens were allowed to stand at 23 ° C. and 50% RH for 48 hours, their physical properties and flame retardance were measured.

Comparative Examples 1 and 2

Comparative Examples 1-2 use each organophosphorus compound independently in the same resin composition as Examples 1-5.

Example Comparative Example One 2 3 4 5 One 2 (A) Polycarbonate resin 76 76 76 76 76 76 76 (B) Vinyl Graft Copolymer 10 10 10 10 10 10 10 (C) vinyl copolymer 14 14 14 14 14 14 14 (D) Organic Phosphorus Compound (D-1) 3 5 7 9 6 12 - (D-2,1) - - - - 3 - - (D-2,2) 9 7 5 3 3 - 12 (E) Fluorinated polyolefin resin 0.5 0.5 0.5 0.5 0.5 0.5 0.5

The physical properties of the specimens molded in Examples and Comparative Examples were measured by the following method.

(1) Flame retardancy was evaluated using a 2.1 mm thick specimen in accordance with UL-94. The total combustion time is the sum of the first and second combustion times when five specimens are evaluated.

(2) Specimens for evaluating the gate impact resistance were fabricated in a 50 × 200 × 3 (mm) sized specimen by residence time in a pin-point gate mold at an injection temperature of 240 ° C using a 10 oz injection machine. It was. Gate impact resistance was assessed by observing the fracture state that occurs when a rounded bottom (R = 5 mm) rod-shaped weight (1 kg) is freely dropped onto a pin point gate of a 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.

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

The compositions and physical properties of the resins prepared in Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 2 below.

From the above results, when the specific monomeric type phosphate ester compound and the phosphate ester morphide compound of the present invention are mixed and used in an appropriate ratio, they are not changed in flame retardancy compared to the case where they are used alone, and the thermal moisture resistance and the gate impact It can be seen that a synergistic effect appears in strength.

The present invention is composed of a polycarbonate resin, a rubber modified vinyl graft copolymer, a vinyl copolymer, a specific monomeric phosphate ester compound, a phosphate ester morphide compound, and a fluorinated polyolefin resin, so that no juice phenomenon occurs and flame retardancy is achieved. The excellent heat and humidity resistance, heat resistance, impact resistance, heat stability, workability and appearance characteristics have the effect of providing a flame retardant thermoplastic resin composition useful for producing an injection molding of a computer monitor exterior or other office equipment.

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

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 these 50 to 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 complex or mixtures thereof 1 to 50 obtained by graft polymerization Part of vinyl graft copolymer; (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 Parts by weight and (C-2) acrylonitrile, methacrylonitrile, C ₁ -C ₈ methacrylic acid alkyl esters, C ₁ -C ₈ acrylic acid methyl esters, maleic anhydride, C ₁ -C ₄ alkyl or phenyl 0-50 parts by weight of a vinyl copolymer or a mixture thereof obtained by copolymerizing 5-50 parts by weight of N-substituted maleimide or a mixture thereof; (D) (D-1) 5 to 95 parts by weight of a monomeric phosphate ester compound represented by the following general formula (I) or a mixture thereof, and (In the above formula (I), R ₁ and R ₂ are each independently a hydrogen atom or methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, isobutyl, isoamyl, t-amyl, etc. Alkyl group, x is an integer of 1-3. (D-2) 5 to 95 parts by weight of a phosphate ester morpholide compound represented by the following general formula (II) or a mixture thereof (In the formula (II), l is 1 or 2, R ₃ , R ₆ and R ₇ are each independently a C ₆ -C ₂₀ aryl or an alkyl substituted C ₆ -C ₂₀ aryl group, R ₄ and R ₅ Are each independently C ₆ -C ₃₀ arylene or an alkyl substituted C ₆ -C ₃₀ arylene group, m and n each represent the number of corresponding repeating units, and m + n in the mixture of phosphate ester morpholide compounds The average value is 0 to 5.) A mixture of organophosphorus compounds having a content of (D) of 1 to 30 parts by weight relative to 100 parts by weight of the constituents (A) + (B) + (C); And (E) Fluorinated polyolefins having an average particle size of 0.05 to 1,000 µm and a density of 1.2 to 2.3 g / cm ³ based on 100 parts by weight of the component (A) + (B) + (C) Suzy; Flame-retardant thermoplastic resin composition, characterized in that consisting of. The method according to claim 1, wherein R ₁ and R ₂ of the monomeric phosphate ester compound (D-1) represented by the structural formula (I) are each a hydrogen atom or an alkyl group such as methyl, ethyl, isopropyl or t-butyl. A flame retardant thermoplastic resin composition characterized by the above. A flame retardant thermoplastic resin composition, wherein X in structural formula (I) is 1 or 2. The phosphate ester morphide compound (D-2) of claim 1, wherein each of R ₃ , R ₆ and R ₇ is a phenyl group; Naphthyl group; Or methyl, ethyl, isopropyl, or t-butyl substituted phenyl group. The flame-retardant thermoplastic according to claim 1, wherein R ₄ and R ₅ of the phosphate ester morphide compound (D-2) represented by the above formula (II) are resorcinol, hydroquinone or bisphenol-A derivatives, respectively. Resin composition. A molded article prepared from the flame retardant thermoplastic resin composition according to any one of claims 1 to 3.