JPH09208841A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin compsn. improved in moldability and flame retardancy by compounding a carboxylated thermoplastic resin with a char-forming resin, a specific nonhalogenated phosphoric ester compd., and an auxiliary flame retardant and/or a melamine compd. SOLUTION: 100 pts.wt. resin compsn. formed from 100 pts.wt. carboxylated thermoplastic resin having a number average mol.wt. of 5,000-1,000,000 and a carboxyl group content of 0.01-40wt.% and 5-95 pts.wt. char-forming resin is compounded with 1-30 pts.wt. nonhalogenated phosphoric ester compd. represented by the formula [wherein R1 to R4 are each (cyclo)alkyl, etc.; X is an arom. group such as a polyhydric alcohol residue; m2 to m4 are each 0 or 1; and (n) is 0-5] and 0.01-30 pts.wt. at least one auxiliary flame retardant selected from among a metal a metal oxide, and a hydrated metal compd. and/or 0.01-20 pts.wt. melamine compd. under the condition that the molar ratio of the phosphoric ester compd. to the carboxyl group of the thermoplastic resin is higher than 0.05 but lower than 10.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition using a halogen-free phosphate ester compound, which is excellent in moldability and flame retardancy.

[0002]

2. Description of the Related Art Synthetic resins are generally light, have excellent water resistance, chemical resistance, electrical insulation, mechanical properties, and are easy to mold and process, so they are used as building materials, electrical equipment materials, automobile materials, fibers. Widely used as a material. However, synthetic resins have a drawback that they are more likely to burn than metallic materials and inorganic materials. Therefore, due to safety concerns, the demand for flame retardancy is increasing, and various flame retardancy standards have been established. Various methods have been proposed as a method for imparting flame retardancy to a flame-retardant synthetic resin, but generally, a halogen compound such as a bromine compound having a high flame retardant effect is used as the antimony oxide if necessary. Is added to the resin. As the bromine compound, nuclear bromine-substituted aromatic compounds such as decabromodiphenyl ether, tetrabromobisphenol A, and brominated phthalimide are known, but the method by adding these flame retardants gives excellent flame retardancy. However, the impact resistance and the heat distortion temperature are lowered, and in some cases, the flame retardant bleeds out on the surface of the resin molded product to deteriorate the appearance of the molded product. In addition, when the resin is molded, the halogen compound is thermally decomposed to generate a gas harmful to the human body, and the mold and the screw are corroded.

[0003] For this reason, methods for flame retardation without using a halogen compound have been studied. As such a method, a method of adding an inorganic flame retardant such as aluminum hydroxide or magnesium hydroxide to the resin (Japanese Patent Application Laid-Open No. 51-132254).
Nos. 56-136832 and 60-13832) are known, but in order to obtain sufficient flame retardancy, it is necessary to add a large amount of the hydrated metal compound,
It has a drawback that the original characteristics of the resin are lost.

On the other hand, as a method not using such a hydrated metal compound, a flame-retardant resin composition comprising a nitrogen-containing compound selected from a vinyl aromatic resin, a polyphenylene ether, an organic phosphorus compound, a triazine and / or a derivative thereof is used. (JP-A-54-38348, JP-A-54-383)
49, European Patent No. 311909), a flame-retardant resin composition comprising polyphenylene ether, a styrene resin and red phosphorus (US Pat. No. 4,461,874), ABS resin with red phosphorus, melamine, and thermal crosslinking. Flame-retardant resin composition containing a curable resin (JP-A-61-2
No. 91643) has been proposed. However,
JP-A-54-38348 and JP-A-54-38.
349, European Patent No. 311909, US Pat. No. 4,461,874 and Japanese Patent Laid-Open No. 61-29.
The resin compositions described in Japanese Patent No. 1643 are useful flame-retardant resin materials containing no halogen compound,
Since polyphenylene ether having low fluidity is mainly used, there is a problem that the moldability of the resin composition is poor.
In addition, in the resin compositions of the above-mentioned U.S. Pat. No. 4,461,874 and JP-A-61-291643, a large amount of red phosphorus is required, so that the resin composition is colored red and a light-colored system is used. There was a problem that it was extremely difficult to match the colors.

Further, as a flame retarding method which is widely used industrially, there is a method of blending an organic phosphate compound such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate and the like with a synthetic resin. . However, such additives conventionally used have drawbacks such as volatilization and smoke generation during molding and during use, and bleeding of a flame retardant on the molding surface. Also, since it is easy to drip when burning,
In order to obtain a V-0 rating in the UL-94 test, it was necessary to add a drip inhibitor such as polytetrafluoroethylene. Further, a method of blending melamine cyanurate with a synthetic resin has been proposed (JP-A-53-31759).
Issue). The resin obtained by this method has no sublimation property,
Bleedout is also improved and has excellent properties, but resin containing melamine cyanurate tends to generate gas in the cylinder of the molding machine during molding, especially during injection molding, so that a satisfactory molded product can be obtained. It is necessary to take many measures such as lowering the molding temperature and shortening the molding cycle. Even if this measure is taken, in light-weight and small-sized thin-walled molded parts, the incidence of defective products such as deformation of molded products and loss of the fine tip portion is high, and the problem of injection moldability has been pointed out.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention does not have the above-mentioned problems, that is, there is no bleeding of the flame retardant at the time of molding, and there is no appearance defect at the time of molding. It is intended to provide a fuel resin composition.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a thermoplastic resin having a carboxyl group and a char-forming resin, and a halogen-free phosphate ester are An excellent flame-retardant effect is exhibited by adding at least one flame-retardant aid and / or melamine compound selected from metals, metal oxides, and hydrated metal compounds to the resin composition obtained in combination. This has led to the completion of the present invention.

That is, the present invention relates to (A) 100 parts by weight of a carboxyl group-containing thermoplastic resin and char-forming resin, and (B) a halogen-free phosphoric ester compound represented by the following formula (1). 1 to 30 parts by weight, and a resin composition of 0.05 <b / a <10, where a and b are the number of moles of the carboxyl group and the organic phosphoric acid compound per unit weight of the resin composition, respectively. (C) at least one flame retardant aid selected from the group consisting of metals, metal oxides and hydrated metal compounds, in an amount of 0.01 to 3
0 parts by weight, and / or (D) the melamine compound is added in an amount of 0.
It is a flame-retardant resin composition obtained by adding 1 to 20 parts by weight.

[0009]

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(Where R is₁, R_Two, R_ThreeAnd R_FourIs each
Independently, alkyl group, alkenyl group, cycloalkyl
Group, alkoxyalkyl group, alkylaryl group, ant
Group, alkoxyaryl group or hydroxyaryl group
Represents a hydroxyl group. X is a polyhydric alcohol residue, or
Nyl group, xylenyl group, ethylphenyl group, isopropyl group
Aromatic group selected from ruphenyl group and butylphenyl group
And m_Two, M_Two, M _ThreeAnd m_FourIs 0 or
Or 1 and n is an integer from 0 to 5. ) Hereinafter, the present invention will be described in detail. First, used in the present invention
The carboxyl group-containing thermoplastic resin will be described.

The thermoplastic resin containing a carboxyl group of the component (A) of the present invention contains a substituent having a carboxyl group in a part or all of the main chain and / or graft chain in the resin. Each of the following resins containing a carboxyl group, polystyrene resin, AS resin, rubber modified polystyrene resin, styrene resin such as ABS resin, polyphenylene ether resin, polycarbonate resin, polyethylene resin, polyolefin resin such as polypropylene, 6-nylon, 6,6-nylon, 6,10-
It is a resin composed of one or a combination of two or more selected from polyamide resins such as nylon and 12-nylon, thermoplastic elastomers, polyethylene terephthalate, polybutylene terephthalate, acrylic resins, polyvinyl alcohol, polyvinyl acetate and polyacetal.

Particularly, a polystyrene resin having a carboxyl group becomes a resin having a high fluidity and a high flame retarding effect by the combination of a char-forming resin, a phosphoric acid ester compound and a flame retardant aid and / or a melamine compound. When used together with the char-forming resin as the component (A) of the invention, an optimum composition as a non-halogen flame retardant material can be obtained.

The polystyrene resin having a carboxyl group is a copolymer of a vinyl monomer having a carboxyl group and a vinyl aromatic monomer, or a resin obtained by covalently bonding a compound having a carboxyl group to polystyrene resin. is there. In the present invention, the vinyl monomer having a carboxyl group is one kind represented by the following general formula (2) having both at least one polymerizable double bond and at least one carboxyl group in one molecule, or It is a mixture of a plurality of compounds.

[0014]

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(In the formula, at least one of R ₅ , R ₆ , R ₇ and R ₈ is a carboxyl group or an organic group having a carboxyl group, and other than that, each independently, hydrogen, halogen atom, carbon number An alkyl group having 1 to 20 (an alkyl group having an alkyl group, an aryl group, a halogen atom, a substituent such as a phosphoric acid ester is also preferable), an unsaturated hydrocarbon group having 2 to 20 carbon atoms (unsaturated hydrocarbon) It is also preferable that hydrogen in the group has an alkyl group, an aryl group, a halogen atom, a substituent such as a phosphoric acid ester, and the like, an aryl group having 5 to 20 carbon atoms (the aryl group is an alkyl group, an aryl group, a halogen atom, Those having a substituent such as a phosphoric acid ester are also preferable.), A cycloalkyl group having 3 to 20 carbon atoms (an alkyl group or an aryl group in the cycloalkyl group,
Those having a substituent such as a halogen atom and a phosphoric acid ester are also preferable. ) A 4- to 14-membered heterocycle (a heterocycle having an alkyl group, an aryl group, a halogen atom, a substituent such as a phosphoric acid ester is also preferable) and the like, R ₅
It is also preferable that ~ R ₈ has a bridge structure. ) Examples of the vinyl monomer having a carboxyl group preferable in the present invention include acrylic acid, methacrylic acid, isocrotonic acid, crotonic acid, maleic acid, fumaric acid and the like. Further, acid anhydrides such as maleic anhydride and fumaric anhydride are also preferably used.

The vinyl aromatic monomer is a mixture of one or more compounds represented by the following general formula (3).

[0017]

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(In the formula, at least one of R ₉ , R ₁₀ , R ₁₁ and R ₁₂ is an aryl group having 6 to 20 carbon atoms (an aryl group is an alkyl group, an aryl group, an alkoxy group, a halogen atom or a phosphoric acid group). Those substituted with an ester or the like are also preferable. Other than that, each independently, hydrogen, a halogen atom, an alkyl group having 1 to 20 carbon atoms (an alkyl group, an aryl group, a halogen atom, a phosphoric acid ester). Those having a substituent such as is also preferable), and an unsaturated hydrocarbon group having 2 to 20 carbon atoms (wherein the hydrogen in the unsaturated hydrocarbon group is a substituent such as an alkyl group, an aryl group, a halogen atom, or a phosphoric acid ester). Some of them are also preferable), aryl groups having 6 to 20 carbon atoms (those having a substituent such as an alkyl group, an aryl group, a halogen atom and a phosphoric acid ester in the aryl group are also preferable), and a carbon number. 20 cycloalkyl group (cycloalkyl group or an aryl group to group, a halogen atom, is preferable that there is a substituent such as phosphoric acid esters), 4
14-membered heterocycle (alkyl or aryl group in the heterocycle,
Those having a substituent such as a halogen atom and a phosphoric acid ester are also preferable. It is also preferable that R _{9 to} R ₁₂ have a bridge structure. ) Specific examples of the vinyl aromatic monomer include styrene and
α-methylstyrene, 3,5-diethylstyrene, 3-
Methyl styrene, 4-methyl styrene, 4-cyclohexyl styrene, 2,4,6-trimethyl styrene, 4-
Phenylstyrene, 2-ethyl-4-benzylstyrene, 7-decyl-1-vinylnaphthalene, 3,6-di-
p-tolyl-1-naphthalene, 2-chlorostyrene, 3
-Chlorostyrene, 4-chlorostyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene,
2,4,5-tribromostyrene and the like can be mentioned. Also, it is preferable that these are one kind or a mixture of two or more kinds. The most preferred vinyl aromatic monomer in the present invention is styrene.

The copolymers of the monomers represented by the above general formulas (2) and (3) can be produced by any known method. In particular, a method of heat-polymerizing a vinyl monomer having a carboxyl group and a vinyl aromatic monomer with an initiator such as an organic peroxide or an azo compound is preferable. Further, as a method for producing a polystyrene resin having a carboxyl group,
A resin in which a carboxyl group is introduced by polymerizing the vinyl aromatic monomer by anionic polymerization and then reacting with carbon dioxide or the like can also be preferably used. The arrangement is not particularly limited and may be alternate, random, block, graft or the like.

As the component (A) of the present invention, a resin obtained by introducing the above vinyl monomer having a carboxyl group into a polystyrene resin by a mechanochemical reaction in an extruder or the like is also preferable. A resin obtained by introducing a vinyl monomer having a carboxyl group into a polystyrene resin by using plasma irradiation or the like is also preferable. The polystyrene resin is a homopolymer obtained from the vinyl aromatic monomer represented by the general formula (3), a copolymer obtained from two or more kinds of vinyl aromatic monomers, or a vinyl aromatic. It is a copolymer of a monomer and another monomer. When a copolymer obtained from two or more vinyl aromatic monomers is used as the polystyrene resin, the main component is preferably a styrene unit. Further, as the vinyl monomer as the other monomer used in the copolymerization, acrylic acid ester such as butyl acrylate, methacrylic acid ester such as methyl methacrylate, α, β-unsaturated nitrile compound such as acrylonitrile and methacrylonitrile,
An N-substituted maleimide such as N-phenylmaleimide can be exemplified. These polymerizations can be carried out by any known method as described above. A particularly preferable polymer among these copolymers is a styrene-acrylonitrile copolymer (AS resin).

The rubber-modified styrene-based resin having a carboxyl group of the component (A) of the present invention is a resin obtained by introducing a carboxyl group into a rubber-modified styrene-based resin. For example, when producing a rubber-modified styrenic resin, a resin or rubber in which a vinyl monomer having a carboxyl group represented by the general formula (2) is introduced into the main chain and / or graft chain by the above-mentioned known method. A resin obtained by introducing a vinyl monomer having a carboxyl group into a modified styrenic resin by a mechanochemical reaction in an extruder or the like, or having a carboxyl group in a rubber-modified styrene resin using radiation, electron beam, plasma irradiation, etc. Examples thereof include resins in which a vinyl monomer has been introduced. The rubber-modified styrene resin means a polymer in which a rubber-like polymer is dispersed in particles in a matrix made of a vinyl aromatic polymer, and an aromatic vinyl monomer is present in the presence of the rubber-like polymer. It can be obtained by bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization according to a known method by adding a vinyl monomer which is copolymerizable with the polymer and, if necessary, a vinyl monomer. Examples of the rubber-like polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the above diene rubbers.
Acrylic rubber such as isoprene rubber, chloroprene rubber, polybutyl acrylate and ethylene-propylene-
Examples thereof include diene monomer-terpolymer (EPDM), and diene rubber is particularly preferable.

If desired, one or more vinyl monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified styrene resin. For example, when it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acnylonitrile and methacrylonitrile can be used. When it is necessary to reduce the melt viscosity at the time of blending, an acrylate ester having an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to enhance heat resistance, a monomer such as acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide or the like may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is 0.
４０40% by weight.

Examples of such resins include impact polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene propylene). Rubber-styrene copolymer) and the like. The polyphenylene ether resin having a carboxyl group of the component (A) of the present invention is a resin obtained by introducing the vinyl monomer having a carboxyl group described above into a polyphenylene ether resin by a mechanochemical reaction or the like in an extruder or the like. is there. Also,
A resin obtained by introducing a vinyl monomer having a carboxyl group into a polyphenylene ether resin by radiation, electron beam, plasma irradiation or the like is also preferable. As the polyphenylene ether resin, a homopolymer or a copolymer having one or more structures represented by the general formula (4) as a repeating unit can be used.

[0024]

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(In the formula, R ₁₃ , R ₁₄ , R ₁₅ , and R ₁₆ are each independently a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, and hydrogen, but all are hydrogen. The production method of the polyphenylene ether resin used in the present invention is not particularly limited, but for example, US Pat.
According to the method described in Japanese Patent No. 788277 (Japanese Patent Publication No. 05-013966), 2,6-xylenol can be produced by oxidative coupling polymerization in the presence of dibutylamine. Also, the molecular weight and the molecular weight distribution are not particularly limited as long as they satisfy the present invention. Typical examples of homopolymers of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,
4-phenylene) ether, poly (2,6-diethyl-)
1,4-phenylene) ether, poly (2-ethyl-)
6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene)
Ether, poly (2-methyl-n-butyl-1,4-phenylene) ether, poly (2-methyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1) , 4-phenylene) ether and the like homopolymers. Among these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable.

The polyphenylene ether copolymer is, for example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or a copolymer of 2,6-dimethylphenol and o-cresol, 2 , 3, 6
Examples thereof include a copolymer of trimethylphenol and o-cresol. The above-mentioned (A) component carboxyl group-containing polycarbonate resin of the present invention is obtained by introducing a carboxyl group-containing vinyl copolymer represented by the general formula (2) into the polycarbonate resin by a mechanochemical reaction or the like in an extruder or the like. Examples thereof include resins and resins obtained by introducing a vinyl monomer having a carboxyl group into a polycarbonate resin by irradiation with radiation, electron beams, plasma, or the like.

As the polycarbonate resin, a polymer having a repeating unit represented by the general formula (5) can be used.

[0028]

[Chemical 6]

(In the formula, Z represents a mere bond, or is an alkylene group having 1 to 8 carbon atoms, alkylidene having 2 to 8 carbon atoms, cycloalkylene having 5 to 15 carbon atoms, SO ₂ ,
It means SO, O, CO, or a group represented by the following general formula (6). X represents hydrogen or a saturated alkyl group having 1 to 8 carbon atoms, and a and b represent an integer of 0 to 4. )

[0030]

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This polycarbonate resin can be obtained, for example, by a solvent method, that is, a known acid acceptor in a solvent such as methylene chloride,
It can be prepared by the reaction of a dihydric phenol with a carbonate precursor such as phosgene or a transesterification reaction of a dihydric phenol with a carbonate precursor such as diphenyl carbonate in the presence of a molecular weight modifier.

The dihydric phenol which can be used here is 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], hydroquinone,
4,4'-dihydroxydiphenyl, bis (4-hydroxyphenylalkane), bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl)
Mention may be made of compounds such as sulfones, bis (4-hydroxyphenyl) sulfoxides, bis (4-hydroxyphenyl) ethers. In particular, it is preferable to use bisphenol A alone or in combination with another dihydric phenol. Further, these dihydric phenols may be homopolymers of dihydric phenols or copolymers or blends of two or more thereof. Further, the polycarbonate resin used in the present invention may be a thermoplastic random branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and / or a carbonate precursor.

The above-mentioned (A) component carboxyl group-containing polyolefin resin of the present invention means, for example, a vinyl resin having a carboxyl group represented by the general formula (2) represented by the general formula (2) mechanochemically added to a polyolefin resin in an extruder or the like. Introducing a carboxyl group by kneading the resin introduced by a reaction, a resin in which a vinyl monomer having a carboxyl group is introduced into a polyolefin resin by radiation, electron beam, plasma irradiation, or the like in air or an oxygen-containing gas. And the like.

As the polyolefin resin, high-density polyethylene, ultra-high-molecular-weight high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene having a specific gravity of less than 0.90, homopolymer such as polypropylene, ethylene, propylene, etc. , A copolymer of two or more compounds selected from other α-olefins, unsaturated carboxylic acids or derivatives thereof, such as ethylene-propylene copolymer, ethylene- (butene-1) copolymer, ethylene- (Meth) acrylic acid copolymer, ethylene- (meth)
Acrylic ester copolymer, polypropylene- (1-
Hexene) copolymer, propylene- (4-methyl-1-)
Pentene) copolymer, poly (4-methyl-1-pentene), polybutene-1 and the like. These can be used alone or in combination.

The carboxyl group-containing polyamide resin of the component (A) of the present invention is, for example, a mechanochemically modified polyamide resin containing a carboxyl group-containing vinyl monomer represented by the general formula (2) in an extruder or the like. Examples of the resin include a resin introduced by a reaction or the like, a resin in which a vinyl monomer having a carboxyl group is introduced into a polyamide resin by radiation, electron beam, plasma irradiation, or the like, or a resin in which a molecular chain terminal is a carboxyl group.

Any polyamide resin may be used as long as it has a bond represented by the formula (7) in the polymer main chain and can be melted by heating.

[0037]

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Specific examples are 4-nylon, 6-nylon, 6,6-nylon, 12-nylon and 6,10.
-Nylon, polyamide obtained from terephthalic acid and trimethylmexamethylenediamine, polyamide obtained from adipic acid and azelaic acid and 2,2-bis (p-aminocyclohexyl) -propane, terephthalic acid and 4,4'- Examples thereof include polyamides obtained from diaminodichlorohexylmethane, and these can be used alone or as a copolymer composed of a combination of two or more kinds thereof, or as a mixture of a homopolymer and a copolymer.

The thermoplastic elastomer having a carboxyl group of the component (A) of the present invention is, for example, a vinyl monomer having a carboxyl group represented by the general formula (2) in a thermoplastic elastomer in an extruder or the like. Examples thereof include resins introduced by mechanochemical reaction and the like, and resins in which a vinyl monomer having a carboxyl group is introduced into a thermoplastic elastomer by radiation, electron beam, plasma irradiation or the like.

As the thermoplastic elastomer, a styrene-butadiene block copolymer, a styrene-butadiene block copolymer in which a part or all of the butadiene moiety is hydrogenated, an ethylene-propylene elastomer,
Styrene-grafted ethylene-propylene elastomer,
Thermoplastic polyester elastomers, ethylene-based ionomer resins, core / shell polymers consisting of a rubber-like core and a non-rubber-like shell, etc., especially styrene-butadiene block copolymer, and part or all of the butadiene moiety is hydrogenated. Preferred are styrene-butadiene block copolymers.

These thermoplastic resins having a carboxyl group may be used alone or in combination of two or more. The resin mixed with the thermoplastic resin having a carboxyl group is not particularly limited, and examples thereof include polystyrene resin and A
S resin, rubber modified polystyrene resin, styrene resin such as ABS resin, polyphenylene ether resin, polycarbonate resin, polyolefin resin such as polyethylene and polypropylene, 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon Examples of the resin include a polyamide resin, a thermoplastic elastomer, polyethylene terephthalate, polybutylene terephthalate, acrylic resin, polyvinyl alcohol, polyvinyl acetate, polyacetal, and the like, or a resin composed of a combination of two or more kinds. However, a combination of known resins in consideration of the physical properties of the obtained resin composition is preferable. For example, for polystyrene resin having a carboxyl group, polystyrene resin, AS resin, rubber modified polystyrene resin, styrene resin such as ABS resin, polyphenylene ether resin, polycarbonate resin, polyphenylene ether resin and styrene resin are used. A resin composition, a resin composition composed of a polyphenylene ether resin and a polyolefin resin, a resin composition composed of a polyphenylene ether resin and a polyamide resin, a resin composition composed of a polyamide resin and a styrene resin, and the like are preferable.

The thermoplastic resin having a carboxyl group has a number average molecular weight of 5,000 to 1,000,000, preferably 10,000 to 500,000. The carboxyl group content in the thermoplastic resin having a carboxyl group is 0.01 wt% to 40 wt%, preferably 0.05 wt% to 30 wt%, and more preferably 0.1 wt% to 30 wt%.
wt% to 20 wt%. Also, the carboxyl group is
It may be contained anywhere in the polymer chain, such as the terminal, branched chain, or main chain.

The above-mentioned (A) component char-forming resin of the present invention is a thermogravimetric analysis measurement (Shimadzu thermogravimetric measuring device DT-3.
0TG-31), the temperature rise rate is 30 ° C / in a nitrogen stream.
The resin has a carbonization residue of 20% by weight or more of the initial weight when the temperature is raised to 800 ° C. in minutes. Examples of such a char-forming resin include poly (2,6-dimethyl-1,4
-Phenylene ether) (hereinafter abbreviated as PPE),
Allylated poly (2,6-dimethyl-1,4-phenylene ether) (hereinafter abbreviated as APPE), poly (2,2)
3,6-trimethyl-1,4-phenylene ether)
(Hereinafter abbreviated as TPPE), 2,6-diphenylpolyphenylene ether (hereinafter abbreviated as TENAX), polyphenyl (hereinafter abbreviated as PPh), polycarbonate (hereinafter abbreviated as PC), polyacrylonitrile (hereinafter abbreviated as PC). PAN), polyether sulfone (hereinafter abbreviated as PES), polyether ketone (hereinafter abbreviated as PEK), polyarylate (hereinafter abbreviated as PAr), polyphenylene sulfide (hereinafter 1M-PPS). Abbreviated), polyimide (hereinafter abbreviated as PI), polyacetonaphthylene (hereinafter PA).
Abbreviated as cNa. ), Phenol novolac (hereinafter P
Abbreviated as Nov. ), T-butyl novolac (hereinafter B
Abbreviated as Nov. ), Cresol novolac, acetylated cresol novolac (hereinafter abbreviated as AcCNov), polybenzyl (hereinafter abbreviated as PBz), polyphenylenediamine terephthalate (hereinafter abbreviated as PPCT), polytetramethylphenylenediamine terephthalate (hereinafter 4M-). PPDT), polytetramethylphenylenediamine isophthalate (hereinafter abbreviated as 4M-PPDI), polymetadiethylbenzene (hereinafter abbreviated as PMEB), and the like, and one selected from these or Two or more kinds can be used in combination.

The most preferable char-forming resin in the present invention is poly (2,6-dimethyl-1,4-phenylene ether) or polycarbonate resin. The char-forming resin in the present invention is preferably 5 to 95 parts by weight with respect to 100 parts by weight of the thermoplastic resin having a carboxyl group.
It is more preferably 5 to 50 parts by weight. Char ratio of pure polymer (ratio of weight after heating to weight before heating)
Using a Shimadzu thermogravimetric analyzer DT-30TG-31, the temperature was raised to 800 ° C. at a heating rate of 30 ° C./min in a nitrogen atmosphere, and the measurement results are shown in FIG.

Further, the halogen-free phosphoric acid ester compound of the component (B) of the present invention means an aromatic system containing a hydroxyl group and / or not containing a hydroxyl group represented by the general formula (1). It is a single substance or a mixture of phosphoric acid esters. Aromatic phosphates that do not contain hydroxyl groups are triphenyl phosphate,
Triallyl phosphates such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate and dicresyl phenyl phosphate and compounds obtained by modifying these with various substituents (for example, resorcinol, bisdiphenyl phosphate, bisphenol A, (Eg, bisdicresyl phosphate) and various condensation type phosphoric acid ester compounds. As the method for producing the phosphoric acid ester compound, for example, phosphorus oxychloride and alcohols and / or phenols are heated and dehydrochlorinated in the absence of a catalyst or in the presence of a Lewis acid catalyst such as aluminum chloride or magnesium chloride. There are ways.

An aromatic phosphoric acid ester containing a hydroxyl group is a phosphorus compound containing one or more phenolic hydroxyl groups in triphenyl phosphate, tricresyl phosphate, etc. shown in the following chemical formulas 9 and 10. It is an acid ester.

[0047]

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[0048]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , A
r ₄ , Ar ₅ and Ar ₆ are a phenyl group, a xylenyl group,
It is an aromatic group selected from an ethylphenyl group, an isopropylphenyl group, and a butylphenyl group, and at least one hydroxyl group is substituted with the above aromatic group in a phosphoric acid ester. Further, n represents an integer of 0 to 3, and m represents an integer of 1 or more. ) A method for producing a hydroxyl group-containing aromatic phosphoric acid ester of the present invention is disclosed in, for example, Japanese Patent Application Laid-Open No. 1-223158, wherein phenol, hydroxyphenol,
Obtained by the reaction of aluminum chloride and phosphorus oxychloride.

The halogen-free phosphoric acid ester compound is preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the component (A) resin. More preferably 5 to 20
Parts by weight. If it deviates from the above range, the flame retardancy or heat resistance is lowered, which is not preferable. Examples of the metal of the flame retardant aid used as the component (C) in the present invention include silver,
Metal powders such as copper, aluminum, iron and nickel can be mentioned. Examples of the metal oxide include aluminum oxide, copper oxide, tin oxide, iron oxide, titanium oxide and the like. The hydrated metal compound, .m hydrated metal compound, in the range of decomposition temperature is 0.99 ° C. to 450 ° C., the general formula _{M m O n · XH 2 O} ( here M is showing a metal, n Is a compound represented by an integer of 1 or more determined by the valence of the metal, and X is a number indicating the bound water contained therein, or a double salt containing the compound. Specifically, for example, aluminum hydroxide ( Al ₂ O ₃ .3H ₂ O or Al (OH) ₃ ), magnesium hydroxide (MgO.H ₂
O or Mg (OH) ₂ ), barium hydroxide (BaO.
H ₂ O or BaO · 9H ₂ O), zirconium oxide hydrate (ZrO · nH ₂ O), tin oxide hydrate (SnO · H)
₂ O), basic magnesium carbonate (3MgCO ₃ · Mg
_{(OH) 2 · 3H 2 O} ), hydrotalcite (6Mg
O ・ Al ₂ O ₃・ H ₂ O), DOUSONAI (NaCO ₃・
Al ₂ O ₃ · nH ₂ O) and the like. These can be used alone or in the form of a mixture of two or more kinds. The most preferable flame retardant aids of the present invention are copper and aluminum oxide. The flame retardant aid is 0.01 to 30 parts by weight, preferably 0.3 to 25 parts by weight, per 100 parts by weight of the resin containing the component (A).

Specific examples of the melamine compound which is the component (D) of the present invention include melamine, melamine cyanurate, methylol melamine, melamine formaldehyde resin and the like. The melamine cyanurate used in the present invention can be produced by any known method. For example, melamine cyanurate is an equimolar reaction product of melamine and cyanuric acid shown in Chemical Formula 10 below, in which an aqueous solution of melamine and an aqueous solution of cyanuric acid are mixed to obtain 90 ° C to 1 ° C.
It is obtained by reacting at 00 ° C. under stirring and filtering the resulting precipitate. It is a white solid and is preferably used in powder form. The most preferred melamine compound of the present invention is melamine cyanurate.

[0052]

Embedded image

In the present invention, the melamine compound is (A)
The amount is 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the component resin. In the flame-retardant resin composition of the present invention, (B) a halogen-free phosphoric acid represented by the following formula (1) with respect to 100 parts by weight of a carboxyl group-containing thermoplastic resin and a char-forming resin. When 1 to 30 parts by weight of an ester compound is contained and the number of moles of the carboxyl group and the phosphate ester compound per unit weight of the resin composition comprising (A) and (B) is a and b, respectively, 0.05 < b /
It is characterized by a <10, but more preferably 0.1 <b / a <5, still more preferably 0.5.
<B / a <5. If the value of b / a is less than 0.05, the flame retardancy is not sufficient, and if it exceeds 10, the appearance at the time of molding becomes poor, which is not preferable.

Further, in the present invention, it is necessary to contain the component (C) in an amount of 0.01 to 30 parts by weight and / or the component (D) in an amount of 0.1 to 20 parts by weight. If it deviates from the above range, the appearance of the molded article will be poor and the heat resistance will be deteriorated. The flame-retardant resin composition of the present invention,
(A) component and (B) component and (C) component and /
Alternatively, the component (D) is a commercially available single-screw extruder, twin-screw extruder,
It can be obtained by, for example, melt-kneading with a heating roll, a kneader, a Banbury mixer, or the like. At that time, the resin composition of the present invention contains an antioxidant such as BHT, an ultraviolet absorber, etc. within a range that does not impair the effects of the invention. Tin-based heat stabilizers, lubricants such as stearic acid and zinc stearate, glass fibers, glass chips, glass beads, carbon fibers, wollast naoto, calcium carbonate, talc, mica, straight powder, fibrous asbestos and other fillers, Reinforcing agents, dyes, pigments and the like can be added as required.

The flame-retardant resin composition of the present invention may contain other flame-retardant agents such as decabromodiphenyl ether, tetrabromobisphenol A, hexabromobenzene, hexabromocyclododecane, perchlorocyclo, within the range that does not impair the effects of the invention. Halogen-containing inorganic compounds such as decane, organic or inorganic phosphorus compounds such as red phosphorus, polyphosphoric acid and ammonium phosphate, halogen-containing phosphorus compounds such as tris (halopropyl) phosphate, tris (haloethyl) phosphate, phosphine chloride Nitrogen-containing phosphorus compounds such as nitrile derivatives and phosphonoamides, nitrogen compounds such as uric acid, dicyandiamide and triazine compounds, antimony oxide, barium metaborate antimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, and molybdic acid compounds. Moniumu, zinc borate, ammonium borate, inorganic compounds such as barium metaborate, polytetrafluoroethylene, may be used in combination anti-drip agent such as a siloxane compound.

By subjecting the composition of the present invention thus obtained to, for example, injection molding or extrusion molding, a molded article having excellent flame retardancy and heat resistance can be obtained.

[0057]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples. The measurements in Examples and Comparative Examples were performed by the following methods. Carboxyl group content measurement method:
The carboxyl group-containing polymer was dissolved in toluene, and the carboxyl group was quantitatively determined by neutralization titration with a phenolphthalein solution and a sodium methylate solution. Flame retardant; VB (Vertical) compliant with UL-94
It was evaluated by the Burning method (1/8 inch test piece).

[0058]

Example 1 Impact-resistant polystyrene resin (hereinafter referred to as HIPS
Is abbreviated. ) (Asahi Kasei Polystyrene Asahi Kasei Corp.) 48 parts by weight, carboxyl group content 8.3 wt.
%, Polystyrene resin having a number average molecular weight of 74000 and a molecular weight distribution of 2.72 (hereinafter referred to as G
It is abbreviated as P. (Asahi Kasei Kogyo KK: Asahi Kasei Polystyrene GP9001) 32 parts by weight, poly 2,6-dimethyl-1,4-phenylene ether (hereinafter referred to as PPE) having an intrinsic viscosity [η] of 0.38 measured in chloroform. 20 parts by weight, 20 parts by weight of triphenyl phosphate (hereinafter abbreviated as TPP) (manufactured by Daihachi Chemical Industry Co., Ltd.), and 0.3 parts of copper powder (manufactured by Wako Pure Chemical Industries, Ltd.).
Parts by weight were mixed and melted for 10 minutes at a melting temperature of 270 ° C. and a rotation speed of 90 rpm using a Labo Plastomill manufactured by Toyo Seiki Seisakusho. A 1 / 8-inch thick test piece was prepared from the polymer composition thus obtained by hot pressing, and flame retardancy was evaluated. The results are shown in Table 1.

[0059]

[Example 2] 48 parts by weight of HIPS and 32 parts of GP9001
A test piece was prepared in the same manner as in Example 1 using 20 parts by weight of PPE, 20 parts by weight of PPE, 20 parts by weight of TPP, and 2.04 parts by weight of copper powder, and flame retardancy was evaluated. The results are shown in Table 1.

[0060]

[Example 3] 48 parts by weight of HIPS and 32 parts of GP9001
By using 20 parts by weight of PPE, 20 parts by weight of PPE, 20 parts by weight of TPP and 2.04 parts by weight of aluminum (manufactured by Wako Pure Chemical Industries, Ltd.), a test piece was prepared in the same manner as in Example 1 and flame retardancy was evaluated. The results are shown in Table 1.

[0061]

[Example 4] 48 parts by weight of HIPS and 32 parts of GP9001
A test piece was prepared in the same manner as in Example 1 by using 20 parts by weight of PPE, 20 parts by weight of PPE, 20 parts by weight of TPP, and 6 parts by weight of alumina (manufactured by Nishio Industry Co., Ltd.), and flame retardancy was evaluated. The results are shown in Table 1.

[0062]

Example 5 48 parts by weight of HIPS and 32 parts of GP9001
A test piece was prepared in the same manner as in Example 1 using 20 parts by weight of PPE, 20 parts by weight of PPE, 20 parts by weight of TPP, and 24 parts by weight of alumina (manufactured by Nishio Industry Co., Ltd.), and flame retardancy was evaluated. Table 1 shows the results
Shown in

[0063]

[Example 6] 48 parts by weight of HIPS and 32 parts of GP9001
A test piece was prepared in the same manner as in Example 1 using 20 parts by weight of PPE, 20 parts by weight of TPE, 20 parts by weight of TPP, and 10 parts by weight of aluminum hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), and flame retardancy was evaluated. The results are shown in Table 1.

[0064]

Example 7 48 parts by weight of HIPS and 32 parts of GP9001
A test piece was prepared in the same manner as in Example 1 using 20 parts by weight of PPE, 20 parts by weight of PPE, 20 parts by weight of TPP, and 25 parts by weight of aluminum hydroxide, and flame retardancy was evaluated. The results are shown in Table 1.

[0065]

Example 8 50 parts by weight of HIPS and 3 parts of GP9001
3.3 parts by weight, PPE 16.7 parts by weight, TPP 2
Using 0.8 parts by weight and 2.3 parts by weight of melamine cyanurate (manufactured by Nissan Chemical Industries, Ltd.), a test piece was prepared in the same manner as in Example 1 and flame retardancy was evaluated. The results are shown in Table 2.

[0066]

[Embodiment 9] 50 parts by weight of HIPS and 3 parts of GP9001
3.3 parts by weight, PPE 16.7 parts by weight, TPP 2
A test piece was prepared in the same manner as in Example 1 using 0.8 parts by weight and 9.1 parts by weight of melamine cyanurate to evaluate the flame retardancy. The results are shown in Table 2.

[0067]

Example 10 48 parts by weight of HIPS and 3 parts of GP9001
2 parts by weight, 20 parts by weight of PPE, 20 parts by weight of TPP,
A test piece was prepared in the same manner as in Example 1 using 6 parts by weight of alumina and 1.2 parts by weight of melamine cyanurate to evaluate the flame retardancy. The results are shown in Table 2.

[0068]

[Embodiment 11] 48 parts by weight of HIPS and 3 parts of GP9001
2 parts by weight, 20 parts by weight of PPE, 20 parts by weight of TPP,
Using 6 parts by weight of alumina and 6 parts by weight of melamine cyanurate, a test piece was prepared in the same manner as in Example 1 and flame retardancy was evaluated. The results are shown in Table 2.

[0069]

[Example 12] 48 parts by weight of HIPS and 3 parts of GP9001
2 parts by weight, 20 parts by weight of PPE, 20 parts by weight of TPP,
Using 10 parts by weight of aluminum hydroxide and 1.5 parts by weight of melamine cyanurate, a test piece was prepared in the same manner as in Example 1 and evaluated for flame retardancy. Table 2 shows the results.

[0070]

Example 13 40 parts by weight of HIPS and 4 parts of GP9001
0 parts by weight, 20 parts by weight of PPE, 20 parts by weight of TPP,
A test piece was prepared in the same manner as in Example 1 using 6 parts by weight of alumina, and flame retardancy was evaluated. Table 2 shows the results.

[0071]

[Example 14] Polycarbonate resin (manufactured by Teijin Chemicals: L
1250: Mw: 26000, MWD: 2.6) 60
Parts by weight, HIPS 36 parts by weight, GP9001 8 parts by weight, PPE 3 parts by weight, TPP 20 parts by weight and alumina 6 parts by weight to prepare a test piece in the same manner as in Example 1 and evaluate the flame retardancy. It was Table 2 shows the results.

[0072]

Comparative Example 1 100 parts by weight of HIPS and 20 parts by weight of TPP were kneaded in the same manner as in Example 1 to prepare a test piece, and flame retardancy was evaluated. The results are shown in Table 3.

[0073]

Comparative Example 2 48 parts by weight of HIPS and 32 parts of GP9001
20 parts by weight of PPE and 20 parts by weight of PPE were kneaded in the same manner as in Example 1 to prepare a test piece, and flame retardancy was evaluated. The results are shown in Table 3.

[0074]

[Comparative Example 3] A flame retardant property was evaluated by preparing a test piece by kneading in the same manner as in Example 6 except that the melamine cyanurate as the component (D) was not used. The results are shown in Table 3.

[0075]

Comparative Example 4 80 parts by weight of HIPS, 20 parts by weight of PPE,
A test piece was prepared in the same manner as in Example 1 using 20 parts by weight of TPP, and flame retardancy was evaluated. The results are shown in Table 3.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

The flame-retardant resin composition of the present invention has flame-retardant properties,
Excellent in moldability, volatilization and smoke emission of flame-retardant material during molding
Since there is no bleeding and there is no appearance defect during molding, it is suitable for home electric appliance parts, OA equipment parts, and the like, and is very useful industrially.

[Brief description of drawings]

FIG. 1 is a diagram showing the results of measurement of the char formation rate of various homopolymers using a Shimadzu thermogravimetric analyzer DT-30TG-31 in a nitrogen atmosphere at a heating rate of 30 ° C./min up to 800 ° C. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/521 KCB C08K 5/521 KCB C08L 101/00 LSY C08L 101/00 LSY

Claims (1)

[Claims] 1. A thermoplastic resin containing a carboxyl group (A)
Of 100 parts by weight of the organic resin and the char-forming resin,
(B) Halogen-free phosphoric acid represented by the following formula (1)
1 to 30 parts by weight of a stell compound, and the resin composition
Carboxyl groups and organic phosphorylation per unit weight
When the mole numbers of the compound are a and b, respectively, 0.0
For the resin composition with 5 <b / a <10, (C) gold
Selected from genus, metal oxides and hydrated metal compounds
0.01 to 30 parts by weight of at least one flame retardant auxiliary,
And / or (D) a melamine compound in an amount of 0.1 to 20% by weight
Flame-retardant resin composition obtained by adding parts. [Chemical 1](Where R₁, R_Two, R_ThreeAnd R_FourEach independently
Alkyl group, alkenyl group, cycloalkyl group, alkoxy group
Cyalkyl group, alkylaryl group, aryl group, ar
Represents a coxyaryl group or a hydroxyaryl group.
X is a polyhydric alcohol residue, or a phenyl group, xyl
Renyl group, ethylphenyl group, isopropylphenyl
Group, an aromatic group selected from a butylphenyl group, and m
_Two, M_Two, M _ThreeAnd m_FourAre each independently 0 or 1.
And n is an integer from 0 to 5. )