JP2002129032A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which does not contain a halogen substantially and which has a heat resistance, especially high deflection temperature under load, and an excellent flame retardance. SOLUTION: The composition substantially comprises (A) a thermoplastic resin (A component) of 80-99.999 wt.%, (B) a metal salt of a specified cyclic phosphate (B component) of 0.001-20 wt.% and (C) a fluororesin (C component) of 0-3 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to flame retardancy, heat resistance,
And a thermoplastic resin composition having excellent impact resistance.

[0002]

2. Description of the Related Art Thermoplastic resins such as polycarbonate resins have good heat resistance, impact resistance, chemical resistance, etc., and are used in a wide range of applications such as electric, electronic equipment, and automobile fields. I have. In addition, for the insufficient properties of the polycarbonate resin alone, ABS resin, a resin composition blended with a styrene-based resin represented by an AS resin and the like are used to reinforce the resin composition. Used in products.

[0003] In recent years, in order to enhance the safety of these products, flame retardancy has been required especially for office automation equipment and home electric appliances.

There are various methods for developing flame retardancy. In the case of a thermoplastic resin, particularly a polycarbonate resin or a resin composition of a polycarbonate resin and a styrene resin, a halogen compound is usually used. And, if necessary, a flame retardant auxiliary such as an antimony compound. However, such a flame retardant generally generates corrosive gas at the time of processing or burning, and thus has a problem of an increase in man-hours due to maintenance of a mold at the time of molding, and in some cases, the environment at the time of product disposal in the future. At present, there is a need for a flame-retardant resin composition that does not contain a halogen-based flame retardant and an antimony compound.

Conventionally, organic phosphorus compounds have been widely used as various non-halogen flame retardants for polycarbonate resins. Such compounds include:
An example is triphenyl phosphate (TPP). However, the addition of TPP lowers the heat resistance of the composition and, because of its high volatility, has a problem that a large amount of gas is generated at the time of extrusion or molding, and contains a halogen-based flame retardant which has been conventionally used. In order to replace the polycarbonate-based flame-retardant resin composition described above, there has been a problem that the decrease in the deflection temperature under load is large and insufficient.

Japanese Patent Application Laid-Open No. 54-157156 discloses that a pentaerythritol diphosphate compound or a pentaerythritol diphosphite compound can be used as a flame retardant for a polycarbonate resin, and these flame retardants have extremely high thermal stability. There is a statement that it is good.

However, when these flame retardants are actually used, although the thermal stability is certainly good and the heat resistance of the resin composition is extremely low, it is necessary to exhibit sufficient flame retardancy. A considerable amount of addition is required, and there has been a problem that mechanical properties are reduced and costs are increased.

On the other hand, Japanese Patent Application Laid-Open No. Hei 9-227772 discloses that a condensed phosphoric ester-based flame retardant, which has been widely used as a flame retardant, is used in combination in order to improve the disadvantages of using such a pentaerythritol diphosphate compound. There is. However, in this publication, it is necessary to add a large amount of condensed phosphoric acid ester having a large decrease in heat resistance in order to ensure sufficient flame retardancy, and a flame-retardant resin composition using a non-halogen compound having sufficient heat resistance Was not obtained.

Japanese Patent Application Laid-Open No. Sho 63-305161 discloses a polyphenylene ether-based resin composition containing metal salts of phosphoric acid esters Ca, Ba and Al as flame retardants. However, even in this publication, a flame-retardant resin having sufficient heat resistance is used because it is a composition in which a phosphoric acid ester (TPP) having a large decrease in heat resistance is used in combination in order to ensure sufficient flame retardancy. No composition was obtained.

[0010] Further, WO 99/36468 discloses that a resin composition comprising a polycarbonate resin, an ABS resin and a metal salt of a phosphate ester is excellent in mechanical properties such as thermal stability and impact resistance. I have.

[0011]

SUMMARY OF THE INVENTION The present invention provides a thermoplastic resin composition which is substantially free of halogen, has heat resistance, especially has a high level of deflection temperature under load, and is excellent in flame retardancy. The purpose is to provide.

The present inventors have conducted intensive studies in order to achieve the above-mentioned object. As a result, surprisingly, the incorporation of a specific metal salt of a cyclic phosphate ester into a thermoplastic resin not only develops flame retardancy but also increases the flame retardancy. It was found that a molded article having excellent heat resistance and impact resistance was obtained, and the present invention was completed.

[0013]

That is, according to the present invention, (A) a thermoplastic resin (A component) 80 to 99.999
% By weight, (B) 0.001 to 20% by weight of a metal salt of a cyclic phosphate (B component) represented by the following general formula (1) and (C) 0 to 3% by weight of a fluororesin (C component). A substantially thermoplastic resin composition is provided.

[0014]

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(Wherein M is a monovalent to trivalent metal atom,
n is the valence of M. Hereinafter, the present invention will be described specifically.

Examples of the thermoplastic resin used as the component A in the present invention include a polycarbonate resin, a styrene resin, an aromatic polyester resin, a polyarylate resin, a polyolefin resin, a diene resin, a polyamide resin, a polyphenylene ether resin, and a polysulfone resin. , A polyphenylene sulfide resin, a polyalkyl methacrylate resin, a thermoplastic polyurethane resin, a thermoplastic polyester elastomer, a polyvinyl chloride resin, a polyacetal resin, a polyether ketone resin, and a polyimide resin. One or more resins selected from the group consisting of an aromatic polyester resin, a polyarylate resin, a polyolefin resin, a diene resin and a polyphenylene ether resin are preferred. In particular, at least 50%, more preferably 60%, even more preferably 70% by weight of the thermoplastic resin.
Desirably, the weight percent is a polycarbonate resin.
Most preferably, the thermoplastic resin is a polycarbonate resin alone or an alloy resin of a polycarbonate resin and a styrenic resin.

The polycarbonate resin is an aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor, or a polyester carbonate resin obtained by reacting a dihydric phenol and an aliphatic diacid with a carbonate precursor. Aromatic polycarbonate resins are preferably used.

Examples of the dihydric phenol used include bis (4-hydroxyphenyl) methane, 1,1'-
Bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2′-bis (4-hydroxyphenyl) butane, 2,2′- Bis (4-hydroxyphenyl) octane, 2,2′-bis (4-hydroxy-3-methylphenyl) propane, 2,2′-bis (4
-Hydroxy-3-tert-butylphenyl) propane, 2,2′-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2′-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2 '
-Bis (4-hydroxy-3-methoxyphenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 1,1'-bis ( 4-hydroxyphenyl) cyclododecane, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxy-3,3'-
Dimethylphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,
Examples include 3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, and 4,4′-dihydroxydiphenyl sulfone. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, with bisphenol A being particularly preferred.

Examples of the aliphatic diacid include those having 8 to 2 carbon atoms.
0, preferably 10-12 aliphatic diacids. Such an aliphatic diacid may be linear, branched or cyclic, and α, ω-dicarboxylic acid is preferred. Examples of preferred aliphatic diacids include straight-chain saturated aliphatic dicarboxylic acids such as decandioic acid, dodecandioic acid, tetradecandiodic acid, octadecandioic acid, eicosandioic acid, and sebacic acid and dodecandioic acid are particularly preferred. preferable.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like. Specifically, phosgene, diphenyl carbonate,
And dihaloformate of dihydric phenol.

In producing a polycarbonate resin,
The above-mentioned dihydric phenols may be used alone or in combination of two or more, and the dihydric phenol and the aliphatic diacid may be used alone or in combination of two or more. Although the content ratio of the dihydric phenol and the aliphatic diacid can be arbitrarily adjusted, it is desirable that at least 40 mol% or more of the polycarbonate resin is derived from bisphenol A. Further, the content of the aliphatic diacid component in the polycarbonate resin is preferably 20 mol% or less from the viewpoint of improving heat resistance and flame retardancy. The polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more polycarbonate resins.

The molecular weight of the polycarbonate resin does not need to be particularly limited, but if it is too low, the strength is not sufficient.
If it is too high, the melt viscosity becomes high and molding becomes difficult. Therefore, it is usually expressed as a viscosity average molecular weight of 10,000 to 50,
000, preferably 15,000 to 40,000. The viscosity average molecular weight (M) here is methylene chloride 1
The specific viscosity (η _SP ) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 00 ml at 20 ° C. was inserted into the following equation. η _SP /C=[η]+0.45×[η] ² C [η] = 1.23 × 10 ^-4 M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration of 0.7)

Next, the basic means for producing a polycarbonate resin will be briefly described. In the interfacial polycondensation method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. When an aliphatic diacid is contained, a method in which such an aliphatic diacid is previously in the form of a salt such as a sodium salt and added to a reaction vessel containing a dihydric phenol can be preferably used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction, and a terminal stopper such as an alkyl-substituted phenol such as phenol or p-tert-butylphenol can be used as a molecular weight regulator. It is desirable to use. Reaction temperature is usually 0 to 40 ° C,
The reaction time is preferably several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. It is not necessary that all of the molecular chain terminals have a structure derived from the terminal stopper.

In a transesterification reaction using a carbonic acid diester as a carbonate precursor (melting method), a predetermined ratio of a dihydric phenol is stirred with a carbonic acid diester while heating in the presence of an inert gas to produce alcohol or phenols. It is performed by the method of distilling. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off alcohol or phenols produced by reducing the pressure from the beginning. A terminal capping agent can be added simultaneously with the dihydric phenol or the like in the initial stage of the reaction or in the middle of the reaction. Further, a catalyst used in a transesterification reaction to promote the reaction can be used. Examples of the carbonic acid diester used in this transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate,
Examples thereof include diethyl carbonate and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred. When an aliphatic diacid is contained, it is preferable that such an aliphatic diacid is previously in the form of an ester such as diphenyl ester.

The styrene resin referred to in the present invention is a homopolymer or a copolymer of styrene derivatives such as styrene, α-methylstyrene and p-methylstyrene, and these monomers and vinyl such as acrylonitrile and methyl methacrylate. Graft copolymer of styrene and / or styrene derivative, or styrene and / or styrene derivative and other vinyl monomer on copolymer with monomer, diene rubber such as polybutadiene, ethylene / propylene rubber, acrylic rubber, etc. It is. Examples of such styrene resins include polystyrene, styrene / butadiene / styrene copolymer (SBS), hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS), and hydrogenated styrene / isoprene / styrene copolymer (SEPS). ), Impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene
Styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene /
Resins such as styrene copolymer (MABS resin), acrylonitrile / acryl rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), and mixtures thereof. The styrenic resin may be one having a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst at the time of its production. Further, in some cases, a polymer and a copolymer having a narrow molecular weight distribution obtained by a method such as anionic living polymerization or radical living polymerization, a block copolymer, and a highly stereoregular polymer or copolymer are used. It is also possible. For the purpose of improving compatibility with the polycarbonate resin, it is also possible to copolymerize the styrene resin with a compound having a functional group such as maleic anhydride or N-substituted maleimide. Among these, high impact polystyrene (HIPS), acrylonitrile
Styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene copolymer (ABS resin) are preferred, and ABS resin is most preferred from the viewpoint of impact resistance. It is also possible to use a mixture of two or more styrene resins.

The ABS resin is a mixture of a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. is there. As the diene-based rubber component forming the ABS resin, for example, a rubber having a glass transition point of 10 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and its ratio is 100% by weight of the ABS resin component. It is preferably from 5 to 80% by weight. Examples of the vinyl cyanide compound grafted to the diene rubber component include acrylonitrile and methacrylonitrile.Examples of the aromatic vinyl compound grafted to the diene rubber component include styrene and α-methylstyrene. Can be mentioned. The content ratio of the vinyl cyanide compound and the aromatic vinyl compound is such that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 100% by weight based on the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Is 95-50
% By weight is preferred. Furthermore, methyl (meth) acrylate,
Ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used.
It is preferably 15% by weight or less in the BS resin. The ABS resin may be produced by any of bulk polymerization, suspension polymerization and emulsion polymerization, and the copolymerization may be carried out in one step or in multiple steps.

The aromatic polyester resin referred to in the present invention is a polymer or a copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid and a diol or an ester derivative thereof as main components.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 1,5-naphthalenedicarboxylic acid are particularly preferably used.

The aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, if it is a small amount, it is also possible to use one or more kinds of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol that is a component of the aromatic polyester of the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-
Examples thereof include aliphatic diols such as propanediol, diethylene glycol, and triethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; and mixtures thereof.

Specific polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, and polybutylene terephthalate (PB).
T), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (P
BN), polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate and the like, as well as copolymerized polyesters such as polyethylene isophthalate / terephthalate and polybutylene terephthalate / isophthalate. Among these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, which have well-balanced mechanical properties and the like, can be preferably used.

According to a method for producing such a polyester resin, a dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc. It is performed by discharging the generated water or lower alcohol out of the system.

As for the molecular weight of the polyester resin, the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.6 to 1.3, preferably 0.75 to 1.3.
1.15.

The polyarylate resin referred to in the present invention refers to a wholly aromatic polyester resin as a whole. The term polyarylate resin may refer only to an amorphous wholly aromatic polyester resin, but in the present invention, includes a type of crystalline polyester resin called a so-called liquid crystal polymer.

The amorphous wholly aromatic polyester resin used in the present invention includes dihydric phenol, or dihydric phenol and hydroquinone and / or resorcinol as a diol component, and terephthalic acid and / or isophthalic acid as a dicarboxylic acid component. Is referred to as a wholly aromatic polyester resin.
As such a dihydric phenol component, a bis (4-hydroxyphenyl) alkane type as described in the description of the polycarbonate resin can be preferably used, and bisphenol A is particularly preferable. Use of hydroquinone and / or resorcinol can be preferably used from the viewpoint of improving the chemical resistance of the resin composition of the present invention. In such a case, the use of hydroquinone is particularly preferred.

One of the preferred embodiments for forming the amorphous wholly aromatic polyester resin and improving the chemical resistance is to use hydroquinone and bisphenol A as a diol component, isophthalic acid as an acid component and hydroquinone as an acid component. And the ratio of bisphenol A is 50/50 to 70 /
And 30 equivalent%. Another aspect useful for increasing the heat resistance temperature of the resin composition of the present invention is a case where bisphenol A is used as a diol component and terephthalic acid is used as an acid component.

The method for producing such an amorphous wholly aromatic polyester is not particularly limited. For example, terephthalic acid chloride or isophthalic acid chloride is used as an acid component, and a reaction is carried out using a catalyst such as a diol component and an alkali component. And an interfacial polymerization method or a method of producing by a solution polymerization method. Further, an aryl terephthalate or a diaryl isophthalate is used as an acid component, and in addition to a titanium compound such as titanium tetrabutoxide, a germanium compound, an antimony compound, and a tin compound already known as a melt polycondensation catalyst for a polyester polymer. And terephthalic acid or isophthalic acid as an acid component, and p-diacetoxybenzene or 2,2'-bis (4-acetoxyphenyl) propane as a diol component. It is possible to appropriately use a melt polymerization method or the like in which a reaction is performed using the above-mentioned melt polycondensation catalyst.

The amorphous wholly aromatic polyester resin of the present invention has an intrinsic viscosity measured at 35 ° C. in a phenol / tetrachloroethane mixed solvent (weight ratio of 60/40), which is different from the viewpoint of heat resistance and moldability. From 0.3 to 1.2, and particularly preferably from 0.4 to 0.9.

The crystalline wholly aromatic polyester resin of the present invention includes one or more dihydric phenols containing no alkylene group, one or more aromatic dicarboxylic acids and / or one or more aromatic dihydroxycarboxylic acids. It is obtained from More specifically, a method of using such a dihydric phenol that does not contain an alkylene group as a derivative such as acetate and increasing the activity of the dihydric phenol, or using such an aromatic dicarboxylic acid as an acid chloride and a phenyl ester And the like, which is obtained by using a derivative having an increased activity of a carboxylic acid as a derivative thereof. Further, those obtained by a method of directly using an aromatic dicarboxylic acid and increasing the activity of the carboxylic acid with a condensing agent such as p-toluenesulfonyl chloride can be used.

Preferred examples of the dihydric phenol containing no alkylene group include 1,4-dihydroxybenzene, 4,4'-dihydroxydiphenyl,
Examples thereof include 2,6-dihydroxynaphthalene and those having an aromatic ring containing one or more non-reactive functional groups such as a lower alkyl group, a halogeno group, and a phenyl group.

The aromatic dicarboxylic acid used in the crystalline wholly aromatic polyester resin of the present invention includes terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
Examples thereof include 4,4-diphenyldicarboxylic acid and those having an aromatic ring containing one or more non-reactive functional groups such as a lower alkyl group, a halogeno group and a phenyl group.

Further, as the aromatic hydroxycarboxylic acid, 1-carboxy-4-hydroxybenzene, 1-carboxy-3-hydroxybenzene, 2-carboxy-
6-Hydroxynaphthalene and its aromatic ring containing one or more non-reactive functional groups such as a lower alkyl group, a halogeno group and a phenyl group are exemplified.

One preferred embodiment of the crystalline wholly aromatic polyester resin of the present invention is 1-carboxy-4-
One in which hydroxybenzene and 2-carboxy-6-hydroxynaphthalene are used in an amount of 70/30 to 85/15 equivalent%. In addition, 1-carboxy-4-hydroxybenzene, 4,4'-dihydroxydiphenyl and terephthalic acid were used in a ratio of 40/30/30 to 30/20/2.
And 0 equivalent%.

The polyolefin resin used in the present invention includes high-density polyethylene resin, low-density polyethylene resin, linear low-density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-acrylic acid. Ester copolymers, ethylene-glycidyl (meth) acrylate copolymers, polypropylene, propylene-vinyl acetate copolymers and the like are desirable.

The diene resin used in the present invention includes
Monomers having a diene structure such as 1,2-polybutadiene resin and trans-1,4-polybutadiene resin alone or copolymers with monomers copolymerizable therewith, and mixtures thereof are exemplified.

The polyphenylene ether resin used in the present invention includes a polymer of 2,6-dimethylphenol,
And a polymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol.
A polymer of dimethylphenol, ie, poly (2,6-
The use of dimethyl-1,4-phenylene ether) is preferred. As the polyphenylene ether resin, for example, a complex obtained by oxidative polymerization of 2,6-xylenol using a complex such as cuprous chloride and pyridine as a catalyst can be used, and the molecular weight of the obtained polyphenylene ether resin is 0.1. 5 g / dl chloroform solution, 30
It is preferable that the reduced viscosity at 0 ° C is in the range of 0.20 to 0.70 dl / g, more preferably 0.30 to 0.70 dl / g.
It is in the range of 0.55 dl / g.

The metal salt of a cyclic phosphate used as the component B in the present invention is a compound having a structure represented by the following general formula (1).

[0048]

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(Wherein M is a monovalent to trivalent metal atom,
n is the valence of M. ) By compounding a metal salt of a cyclic phosphate,
In addition to imparting flame retardancy to the resin, the deflection temperature under load of the resin itself may not substantially decrease or may increase.

Examples of the metal salt of the cyclic phosphate represented by the general formula (1) include, for example, 2,4,8,10-
Sodium salt of tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate;
Potassium salt of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate, 2,4,8,10-tetraoxa-3,
9-diphosphaspiro [5,5] undecane-3,9-
Calcium salt of diphosphate, magnesium salt of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate,
Aluminum salt of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate, 2,4,8,10-tetraoxa-
3,9-diphosphaspiro [5,5] undecane-3,
Barium salt of 9-diphosphate, 2,4,8,10-
Zinc salt of tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate, 2,4
And tin salts of 8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate. Of these, in particular 2,4,8,1
0-tetraoxa-3,9-diphosphaspiro [5,
5] The calcium salt of undecane-3,9-diphosphate is preferred.

As a method for synthesizing the metal salt of the cyclic phosphate represented by the above formula (1) of the present invention, for example, pentaerythritol is reacted with phosphorus oxychloride,
3,9-dichloro-2,4,8,10-tetraoxa-
3,9-diphosphaspiro [5,5] undecane-3,
9-Dioxide is obtained, which is reacted with N, N-dimethylsulfoxide to give 2,4,8,10-tetraoxa-
3,9-diphosphaspiro [5,5] undecane-3,
A method of obtaining an N, N-dimethylsulfoxonium salt of 9-diphosphate and further reacting the obtained compound with a metal carbonate can be preferably employed.

The fluororesin optionally used as the component C in the present invention contains a fluorine atom and has a fibril-forming ability, and is used as an ignition agent and an agent for preventing dripping of a melt. . Such fluororesins include:
For example, homo- or copolymers of fluorine-containing monomers such as tetrafluoroethylene, trifluoroethylene, vinyl fluoride, vinylidene fluoride, and hexafluoropropylene may be mentioned. The fluorine-containing monomer and a polymerizable monomer such as ethylene, propylene, and acrylate may be copolymerized within a range that does not impair the dropping prevention performance. Among these fluororesins, polytetrafluoroethylene is preferred. The preferred polytetrafluoroethylene is what is called type 3 according to the ASTM standard.

The fluororesin can be produced by a conventional method, for example,
It can be obtained by the emulsion polymerization method described in U.S. Pat. No. 2,393,967. The fluororesin can be used in a solid state or an emulsion state, but in the composition of the present invention, it is preferable to use the solid state in view of the thermal stability of the resin.

Next, the content of each component will be described. The flame-retardant polycarbonate-based resin composition of the present invention is characterized in that the total of the components A, B and C is 100% by weight.
A component 80 to 99.999% by weight, B component 0.001 to
It consists essentially of 20% by weight and 0-3% by weight of component C. If the B component is less than 0.001% by weight, the flame-retardant effect becomes insufficient, and if it is more than 20% by weight, scorching occurs at the time of molding the resin, and the physical properties of the resin are impaired.

The component A is preferably 90 to 99.99% by weight based on 100% by weight of the total of the components A, B and C.

The component B is preferably from 10 to 0.01% by weight based on 100% by weight of the total of the components A, B and C.

Component C is preferably from 0.1 to 2% by weight, more preferably from 0.2 to 1% by weight, with the total of components A, B and C being 100% by weight. By blending the C component with the resin in this range, the drip prevention effect is excellent, and the appearance of the resin molded article is less likely to be uneven, and the appearance is excellent.

The flame-retardant resin composition of the present invention contains a phosphorus compound other than the component B of the present invention, which is conventionally known as one which imparts flame retardancy to a resin within a range not to impair the object of the present invention. It is also possible to use acid esters, red phosphorus, metal salts of sulfonic acids, and silicone-based flame retardants.

Further, for the purpose of improving the impact resistance, an elastic elastomer such as an acrylic elastomer, an elastomer having an IPN structure in which an acrylic polymer and a polyorganosiloxane polymer have an IPN structure, a thermoplastic polyurethane elastomer, a thermoplastic polyester elastomer, and a thermoplastic polyamide elastomer. It is also possible to add further coalescence.

Also, various additives such as antioxidants, ultraviolet absorbers, deterioration inhibitors such as light stabilizers, lubricants,
Antistatic agents, release agents, plasticizers, sliding agents, reinforcing fibers such as glass fibers, carbon fibers, aramid fibers, aromatic polyester fibers, fillers such as talc, mica, wollastonite, glass flakes, pigments, etc. May be added.
The amount of the additive to be used can be appropriately selected according to the type of the additive within a range not impairing the heat resistance, impact resistance, mechanical strength, and the like.

The flame-retardant resin composition of the present invention is usually prepared by feeding a thermoplastic resin, a metal salt of a cyclic phosphate, a fluororesin and other components from separate feeders, or part or all of these components. Is prepared by supplying a mixture preliminarily mixed with a mixer and each component other than the mixture to a kneader from each supply machine and melt-mixing. Examples of the mixer include a tumbler, a V-type blender, a super mixer, a super floater, and a Henschel mixer. As the mixer, various melt mixers can be used. For example, a kneader, a single-screw or twin-screw extruder can be used. Among them, a method in which the resin composition is melted and extruded using a twin-screw extruder or the like and pelletized by a pelletizer is preferably used. In this case, for example, 200 to 32
It is preferable to use an extruder having one or more degassing holes at a temperature of 0 ° C., preferably about 220 to 290 ° C., and to perform melt kneading under reduced pressure.

The flame-retardant resin composition of the present invention is useful as a material for forming various molded articles such as housings and enclosures for home electric appliances and OA equipment, and housings and casings for portable information equipment and the like. Such a molded product is a conventional method, for example, a pellet-shaped flame-retardant resin composition,
It can be manufactured by injection molding at a cylinder temperature of, for example, about 220 to 290 ° C. using an injection molding machine.

[0063]

EXAMPLES The present invention will be described below with reference to examples.
The scope of the present invention is not limited to these examples.

Reference Example (Synthesis of Metal Salt of Cyclic Phosphate Ester) Pentaerythritol 20 was placed in a 5-liter three-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and an oil bath.
4.2 g (1.5 mol), phosphorus oxychloride 920.0
g (6.0 mol) and 5.48 g (0.075 mol) of N, N-dimethylformamide were charged and reacted at a reaction temperature of 40 ° C. for 6 hours under a nitrogen stream. The generated hydrogen chloride was absorbed into a sodium hydroxide aqueous solution outside the reaction system through a reflux condenser. After the completion of the reaction, most of the excess phosphorus oxychloride was distilled off, and the remaining white product was washed with methylene chloride and dried to give 3,9-dichloro-2,4,8,10-tetraoxalic acid. 356.4 g of -3,9-diphosphaspiro [5,5] undecane-3,9-dioxide was obtained (80% yield).

Next, a stirrer, a reflux condenser, a dropping funnel,
In a 5 liter three-necked flask equipped with an oil bath, N, N
-Dimethyl sulfoxide 904.2 g (11.6 mo
l) and cooled to 18 ° C. to give compound 3 obtained by the above method.
00.1 g (1.01 mol) was added little by little so as to keep the reaction temperature at 25 ° C. or lower, and the mixture was reacted for 1 hour. Chloroform was added to the white slurry after the reaction, and a white product was separated by filtration and further washed with chloroform. The resulting white product is dried and the N, N-dimethylsulfoxonium salt of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate 339. 5 g were obtained (yield 100
%).

Subsequently, 336.2 g (1.00 mol) of the compound obtained by the above method was placed in a 10 L three-necked flask with 5 L of water.
And dissolved in calcium carbonate 122.1 g (1.22 m
ol) and reacted until the generation of bubbles ceased. After completion of the reaction, excess calcium carbonate was removed by a glass filter, and methanol was added to the filtrate to precipitate a white product. The precipitate was filtered off by suction filtration, dried, and 286.2 g of calcium salt of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane-3,9-diphosphate (yield) 96%).

[Examples 1 to 3, Comparative Examples 1 to 4] Tables 1 and 2
0.05 parts by weight of trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.) as a stabilizer was added to each of the components described and a total of 100 parts by weight of each of the components, and the mixture was uniformly mixed using a tumbler. After that, a twin screw extruder with a 15 mmφ vent (KZW-15 manufactured by Technovel Corp.)
The resin was pelletized at a resin temperature of 260 ° C., and the obtained pellet was dried at 95 ° C. for 4 hours with a hot air drier. Each test piece was molded from the pellets using an injection molding machine (J75Si manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C.

(1) Flammability The flammability was evaluated using a 3.2 mm thick test piece according to the vertical burn test specified in UL-94 of the US UL standard as an evaluation scale of flammability.

(2) Heat resistance (deflection temperature under load) The deflection temperature under load (HDT) was measured in accordance with JIS K7207 under a load of 1.81 MPa (18.5 kgf / c).
m ² ). In addition, the symbol which shows each component of Table 1 and 2 is as follows.

(A component) Polycarbonate resin PC; polycarbonate resin (Panlite L-1225WP, manufactured by Teijin Chemicals Limited, viscosity average molecular weight 22,50)
0) ABS; ABS resin (Santac U manufactured by Mitsui Toatsu Co., Ltd.)
T-61) (Component B) Metal salt of cyclic phosphate FR-Ca; 2,4,8,10-tetraoxa-3,9
-Calcium salt of diphosphaspiro [5,5] undecane-3,9-diphosphate

(Phosphate ester other than component B) TPP; triphenyl phosphate (S-4, manufactured by Daihachi Chemical Co., Ltd.) PX-200; condensed phosphate ester {resorcinol-bis manufactured by Daihachi Chemical Co., Ltd. (Dixylyl phosphate)
Product name PX-200

(Component C) Fluororesin PTFE; Polytetrafluoroethylene (Polyflon FA500 manufactured by Daikin Industries, Ltd.)

[0073]

[Table 1]

[0074]

[Table 2]

As is clear from Tables 1 and 2, FR
It can be seen that the molded article to which -Ca was added exhibited a flame retardant effect. Further, as shown in Examples 1 and 2, FR-
Surprisingly, even in a molded article to which a small amount of Ca is added (0.5% by weight), a flame retardant effect is exhibited. Furthermore, it can be seen that the use of the metal salt of the cyclic phosphoric ester suppresses the decrease in the deflection temperature under load, which is generally a problem with phosphorus-based flame retardants. Example 3 and TPP and P
When the deflection temperatures under load of the molded products (Comparative Examples 3 and 4) to which X-200 is added are compared, the effect is clear. Such an effect is particularly useful for office automation equipment and home electric appliances that require heat resistance of the thermoplastic resin.

[0076]

Industrial Applicability The resin composition of the present invention exhibits flame retardancy without containing a halogen-based flame retardant in a polycarbonate-based thermoplastic resin composition, and is further compared with a case where a conventional phosphorus-based flame retardant is used. The deflection of load deflection temperature is extremely small, and the properties such as impact resistance are also excellent.
It is particularly useful for A devices, home appliances, and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AA011 AC001 BB001 BC021 BD031 BD122 BD142 BD152 BD162 BG051 CB001 CF001 CF161 CG001 CH071 CH091 CK021 CL001 CM041 CN011 CN031 EW046 FD136

Claims (4)

[Claims] (A) a thermoplastic resin (A component) 80 to 9
9.999% by weight, (B) a metal salt of a cyclic phosphate ester represented by the following general formula (1) (component B) 0.001 to 2
A thermoplastic resin composition consisting essentially of 0% by weight and (C) 0 to 3% by weight of a fluororesin (component (C)). Embedded image (Where M is a metal atom having 1 to 3 valences, and n is a valence of M.) 2. The thermoplastic resin of component A is one or more kinds of heat selected from polycarbonate resin, styrene resin, aromatic polyester resin, polyarylate resin, polyolefin resin, diene resin and polyphenylene ether resin. The thermoplastic resin composition according to claim 1, which is a thermoplastic resin. 3. At least 50 of the thermoplastic resin of component A
The thermoplastic resin composition according to claim 1, wherein the weight% is a polycarbonate resin. 4. The metal salt of the cyclic phosphate represented by the general formula (1) of the component B, wherein the metal atom of the formula M comprises sodium, potassium, calcium, magnesium, barium, zinc and aluminum. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is at least one metal atom selected from the group.