JP2002265800A - Flame-retardant synthetic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-crystalline synthetic resin composition comprising a phosphoric ester flame retardant which has good mechanical properties and excellent flame retardance. SOLUTION: As a flame retardant auxiliary, an organic phosphoric ester zirconium salt compound is compounded with a non-crystalline synthetic resin comprising a phosphoric ester flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant synthetic resin composition having improved flame retardancy, and more particularly, to a non-crystalline synthetic resin containing a phosphate ester-based flame retardant. The present invention relates to a flame-retardant synthetic resin composition in which an ester zirconium salt compound is blended as a flame-retardant aid and having improved flame retardancy.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate resins and AB
A multi-component polymer compound mixed with a styrene-based resin having excellent impact resistance such as S and AS is excellent in weather resistance, heat resistance and impact resistance.
It is widely applied as a housing material in the field of OA equipment such as copiers, printers, facsimiles, personal computers, etc. It is also expected as a substitute for metal products in the field of automobile parts.

[0003] In addition, molded articles using these synthetic resin compositions are required to have flame retardancy. The flame retardancy is determined by subject 94 (Underwriters Laboratories, a US flame retardant standard). Hereinafter, it is referred to as UL-94V.). In UL-94V, the flame retardancy is evaluated based on the quenching time until natural extinguishing after ignition of the test piece and the presence or absence of resin dripping (drip) due to combustion, and there is no drip in the synthetic resin composition for the above application. It is required that the extinction time be short.

As a flame retardant for imparting flame retardancy to a synthetic resin composition, a system in which a halogen-based organic compound and antimony trioxide are combined has conventionally been used. In view of toxic gas generated at the time of incineration and environmental problems, those containing no halogen are required.

[0005] In order to solve the above problems, a method of using a phosphorus-based flame retardant represented by an aromatic phosphate ester in a polycarbonate resin or a multi-component polymer compound of the polycarbonate resin and a styrene resin has been studied. . For example, U.S. Pat. No. 5,204,394, U.S. Pat. No. 5,112,556, and JP-A-5-26294.
0, JP-A-7-26129, JP-A-10-
168273 discloses the use of phosphate ester flame retardants.

However, since a large amount of the phosphoric ester-based flame retardant is required to obtain high flame retardancy, the physical properties of a molded article may be affected. It was difficult to be satisfied.

JP-B-42-9006 discloses that a metal salt of an organic phosphate is added to a synthetic resin. JP-B-48-29614 discloses a metal salt of a phosphite compound and an organic phosphate. It is described that the resin is used to make the resin flame-retardant. Also, JP-A-2-180
No. 956 describes that an organic phosphate metal salt is added to a polycarbonate resin. Further, Japanese Patent No. 2581777 discloses a flame-retardant polycarbonate resin composition using a phosphate metal salt for a polycarbonate resin. However, the techniques described in these publications are inadequate when the amount of the phosphoric acid ester metal salt used is small, and in the case of a multi-component polymer compound further containing a styrene resin,
When the effect is completely insufficient and the amount of the phosphoric acid ester metal salt used is large, dripping becomes severe. Japanese Patent Application Laid-Open No. 5-156078 discloses that an organic zirconium phosphate and another flame retardant are added to a crystalline synthetic resin, but there is no description about an amorphous synthetic resin. Was.

Accordingly, an object of the present invention is to provide a flame-retardant synthetic resin composition having good physical properties and excellent flame retardancy in a non-crystalline synthetic resin composition.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, by adding an organophosphate zirconium salt compound as a flame retardant auxiliary, the physical properties were impaired. The present inventors have found that high flame retardancy can be imparted without using a large amount of a phosphate ester-based flame retardant, and reached the present invention.

That is, the present invention relates to (A) 100 to 100 parts by weight of an amorphous synthetic resin, (B) 0.5 to 30 parts by weight of a phosphate ester-based flame retardant represented by the following general formula (1) and ( C) An object of the present invention is to provide a flame-retardant synthetic resin composition containing 0.05 to 5 parts by weight of an organic phosphate ester zirconium salt compound.

[0011]

Embedded image (Wherein R ₁ , R ₂ , R ₄ and R ₅ are the same or different and represent an alkyl group having 1 to 10 carbon atoms or an aromatic group represented by the following general formula (2). R ₃ Represents a divalent aromatic group represented by the following general formula (3) or (4).
Indicates 0 to 10. )

Embedded image (Wherein A ₁ and A ₂ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and A ₃ , A ₄ , A ₅ , A ₆ , A ₇ and A _{And 8} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a halogen atom or a cyano group. , A sulfone group, an alkylidene group having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms.)

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant synthetic resin composition of the present invention will be described in detail below.

The (A) non-crystalline synthetic resin used in the present invention includes polycarbonate resins such as thermoplastic aromatic polycarbonate and branched polycarbonate; polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile butadiene styrene (ABS) resin. , Polyethylene chloride acrylonitrile styrene (AC
S) resin, styrene acrylonitrile (SAN) resin,
Acrylic nitrile butyl acrylate styrene (AA
S) Styrene resins such as resin, butadiene styrene resin, styrene maleic resin, styrene maleimide resin, ethylene propylene acrylonitrile styrene (AES) resin, butadiene methyl methacrylate styrene (MBS) resin; and polyphenylene ether (PPE) as another resin Resin, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer Halogen-containing copolymers, such as vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-cyclohexylmaleimide copolymer Butter, petroleum resins, coumarone resins, polystyrene, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polycarbonate /
Examples include thermoplastic resins such as ABS resins, polyacetals, polyurethanes, and fibrous resins, and blends thereof, and thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins. Further, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used. The non-crystalline synthetic resin used in the present invention may be a mixture of these non-crystalline synthetic resins alone or in combination of two or more. Further, the non-crystalline synthetic resin and a small proportion of polypropylene, polyethylene terephthalate (PET) or A mixture of crystalline synthetic resins such as polybutylene terephthalate (PBT) may be used. Among the above-mentioned non-crystalline synthetic resins, polycarbonate-based resins, particularly styrene-based resins, and polyphenylene ether-based resins, which are difficult to flame retardant,
Alternatively, a mixture thereof is preferably used.

The above-mentioned polycarbonate resin is a polymer having a carbonate bond, which contains two or more hydroxyl groups, each of which is directly bonded to an aromatic carbon atom. Group compounds (hereinafter, referred to as
It is referred to as a polyvalent hydroxy aromatic compound. )) And the carbonate precursor. The polycarbonate resin is not particularly limited by its structure, production method, chain terminator, molecular weight and the like, and may be branched. In addition, one kind or a mixture of two or more kinds may be used, and further, for example, a polymer component used by mixing with a well-known general polycarbonate such as polyester may be included.

The polycarbonate resin is generally obtained from a dihydroxy aromatic compound and a carbonate precursor, and is represented by the following general formula (8).

[0016]

Embedded image (In the formula, A represents a residue of a dihydroxy aromatic compound used in the polymerization reaction represented by the following formula (a) or (b).)

Embedded image (Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom,
Represents a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group or an alkylaryl group,
m, m ′ and m ″ each independently represent an integer of 0 to 4,
q represents an integer of 0 to 2, X is an alkylene group, a cycloalkylidene group, a single bond, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-or -C
(= O)-. )

In the general formula (8), examples of the halogen atom represented by R ₈ , R ₉ and R ₁₀ include fluorine, chlorine, bromine and iodine, and examples of the alkyl group include methyl, ethyl, propyl and Isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl and the like. Examples of the alkoxy group include groups derived from these alkyl groups, examples of the cycloalkyl group include cyclobutane, cyclopentane, cyclohexane or a substituted product thereof, and examples of the aryl group include phenyl,
Methylphenyl, dimethylphenyl, ethylphenyl,
Octylphenyl, chlorophenyl, bromophenyl,
Naphthyl and the like, and as the alkylaryl group,
Benzyl, phenethyl and the like. Examples of the alkylene group represented by X include methylene, ethylene, ethane-1,1-diyl, propylene, and propane-2,2-
Diyl, 1-methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 2,2-dimethylpropylene, 1,3-dimethylpropylene, butylene,
-Methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene and the like, and as the cycloalkylidene group, Examples thereof include cyclopentylidene, cyclohexylidene and substituted products thereof.

The polyhydric hydroxyaromatic compound used as a raw material of the polycarbonate resin includes those corresponding to the above general formula (8). Specifically, resorcin, catechol, hydroquinone, 3-methylresorcin, 3-ethyl resorcinol, 3-propyl resorcinol, 3-butyl resorcinol, 3-tert-butyl resorcinol, 3-phenyl resorcinol, 3-cumyl resorcinol,
Dihydroxybenzenes such as 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-tert-butylhydroquinone, 3-phenylhydroquinone, and 3-cumylhydroquinone; 4,4′-dihydroxydiphenyl Bishydroxyaryls such as 1,1-bis (4-hydroxyphenyl) -2,4,4-trimethylcyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4- Hydroxyphenyl)
-3,3-dimethylcyclohexane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3,
5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-
Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane and 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,4-bis (4-hydroxyphenyl Bis (hydroxyaryl) aryls such as sulfonyl) benzene and 4,4-bis (4-hydroxyphenylsulfonyl) benzene; bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl)
Ethane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-chloro -4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-
Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,
2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2-bis (4-
Hydroxyphenyl-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methoxyphenyl) propane, 1,1 −
Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxy) butane, 2,4-bis (4-hydroxyphenyl-2-methyl) butane and the like Bis (hydroxyaryl) alkanes; dihydroxyaryl ketones such as bis (4-hydroxyphenyl) ketone and bis (4-hydroxy-3-methylphenyl) ketone;
4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether,
Dihydroxyaryl ethers such as 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether;
4,4'-thiodiphenol, bis (4-hydroxyphenyl) sulfide, 4,4'-dihydroxy-3,
3′-dimethyldiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfoxide, 2,2-bis (4-hydroxyphenyl) Examples include dihydroxyaryl sulfur compounds such as sulfone, 4,4'-dihydroxydiphenylsulfone, and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, and phenolphthalein, and correspond to the general formula (8). Examples other than those that do
2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobis (1H-indene)-
Examples thereof include those having a condensed ring such as 7,7′-diol, which may be used alone or as a mixture of two or more kinds, and further used in a mixture with a trivalent or more polyvalent hydroxy aromatic compound. Is also good.

Examples of the carbonate precursor which is a raw material of the polycarbonate resin include carbonyl halide, carbonyl ester, haloformate and the like. Preferred specific examples are phosgene, carbonate diester, diphenyl carbonate, dihydric phenol and the like. And mixtures thereof.

The molecular weight of the polycarbonate resin is as follows:
If it is less than 10,000, the impact strength of the formed article may decrease. If it exceeds 200,000, the fluidity may decrease and processing may become difficult. More preferred.

For the above reasons, a chain terminator may be used to control the molecular weight during the production of the polycarbonate resin. In this case, examples of the chain terminator used include phenol, p-chlorophenol, p-tert-butylphenol, 2,4,6-tribromophenol, 4- (1,3-tetramethylbutyl) phenol and the like. Long-chain alkylphenols; 3,5-ditert-butylphenol, p-isooctylphenol, p
Tertiary octylphenol, p-dodecylphenol,
2- (3,5-dimethylheptyl) phenol, 4-
A phenolic compound such as (3,5-dimethylheptyl) phenol may be used, and a general amount of the phenolic compound is 0.5 to 10 of the polyhydric hydroxyaromatic compound diphenol used.
Mol%.

In the multi-component polymer compound comprising a polycarbonate-based resin and a styrene-based resin used as the non-crystalline synthetic resin in the present invention, the styrene-based resin constituting the multi-component polymer is an aromatic represented by styrene. A polymer compound obtained by using a vinyl compound as an essential raw material and another resin raw material as an optional component, and these can be used without any particular restrictions on the structure, production method, molecular weight and the like.

Examples of the aromatic vinyl compound used as an essential raw material of the styrene resin include styrene, vinylnaphthalene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and ethylstyrene. A halogen atom and / or an alkyl group and / or an alkenyl group such as monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene and p-tert-butylstyrene.
A 5-substituted styrene-substituted product is mentioned, and as a resin raw material used as an optional component, vinyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid,
Α, β-unsaturated carboxylic acids such as methacrylic acid; α, β-unsaturated carboxylic esters such as alkyl acrylates having 1 to 8 carbon atoms and alkyl methacrylates having 1 to 8 carbon atoms; maleic anhydride, itacone anhydride Α, β- such as acids
Unsaturated dicarboxylic anhydrides and derivatives thereof; α, β-unsaturated carboxylic acid imides such as maleimide, N-maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and No-chlorophenylmaleimide Conjugated diene compounds such as isoprene, butadiene and chloroprene; epoxy-modified conjugated diene compounds;
Olefins such as ethylene and propylene; and vinyl acetate.

The styrene-based resin only needs to use at least one kind of the above-mentioned aromatic vinyl compound, and may be a mixture of two or more kinds of polymer compounds. As a method for producing a mixture of two or more kinds, a blending method such as a melt blending method, a kneading blending method, a melt casting method, a solution method, a copolymerization method such as a grafting method, a block method, a random method, a mutual method, a melt grafting method, etc. And a block graft copolymerization method.

The type and amount of the styrenic resin are appropriately selected depending on the physical properties of the desired molded product. ABS resin is suitable for housing materials and automotive parts, and the amount of the styrene resin is polycarbonate. 1 for resin
It is preferably from 70 to 70% by weight, more preferably from 10 to 50% by weight.

The multi-component polymer compound comprising a polycarbonate resin and a styrene resin used as the non-crystalline synthetic resin in the present invention is not particularly limited by the production method, molecular weight and the like.

Further, the polyphenylene ether-based resin used as the non-crystalline synthetic resin in the present invention is a homopolymer or a copolymer having a structural unit represented by the following general formula (9) or (10) as a repeating unit. It is a polymer.

[0028]

Embedded image(Where R₁₁, R₁₂, R₁₃, R₁₄, R₁₅And R₁₆Is charcoal
An alkyl group having 1 to 4 atoms, an aryl group, a halogen atom
And a monovalent residue such as a hydrogen atom,₁₅And R ₁₆Is the same
Sometimes not a hydrogen atom. )

A typical example of the homopolymer of the polyphenylene ether resin is poly (2,6-dimethyl-
1,4-phenylene ether, 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-6-n-butyl-1, 4-phenylene) ether, poly (2-ethyl-
6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly Homopolymers such as (2-methyl-6-chloroethyl-1,4-phenylene) ether are exemplified.

Further, the copolymer of the above polyphenylene ether resin is composed of 2,6-dimethylphenol and 2,3,3-dimethylphenol.
Copolymer of 6-trimethylphenol, copolymer of 2,6-dimethylphenol and o-cresol, 2,6
And polyphenylene ether copolymers mainly composed of a polyphenylene ether structure, such as copolymers of dimethylphenol with 2,3,6-trimethylphenol and o-cresol.

Further, the styrene resins mentioned above can be used together with the above polyphenylene ether resins.

The phosphoric ester flame retardant (B) used in the present invention is a compound represented by the general formula (1). In the general formula (1), R ₁ , R ₂ , R ₄ and Examples of the alkyl group having 1 to 10 carbon atoms represented by R ₅ and the alkyl group having 1 to 10 carbon atoms represented by A ₁ and A ₂ in the general formula (2) include methyl and ethyl. Propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl, decyl and the like. Examples of the halogen atom represented by A ₁ and A ₂ include a fluorine atom, a chlorine atom, and a bromine atom. Also, A ₃ , A ₄ , A ₅ , A ₆ , A 3 in the general formulas (3) and (4)
Examples of the alkyl group having 1 to 4 carbon atoms represented by ₇ and A ₈ include methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, and tert-butyl. Examples of the cycloalkyl group include cyclohexyl. And the like.Examples of the aryl group include phenyl, cresyl, xylyl,
2,6-xylyl, 2,4,6-trimethylphenyl,
Examples include butylphenyl and nonylphenyl, and examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Further, the number of carbon atoms represented by B in the general formula (4) is 1
Examples of the alkylidene group having 5 to 5 include ethylidene and isopropylidene, and examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, trimethylene and tetramethylene.

The method for producing the phosphate ester-based flame retardant is not particularly limited, and any known method can be used. For example, a method of performing a dehydrochlorination reaction between phosphorus oxychloride and each phenol compound in the presence of a Lewis acid catalyst,
A method of reacting phosphorus oxychloride with a monohydric phenol compound and then reacting with a dihydric phenol compound, a method of reacting phosphorus oxychloride with a dihydric phenol compound and then reacting with a monovalent phenol compound, A method of transesterifying phenyl phosphate with a polyhydric phenol such as resorcinol may be used. These reactions are preferably performed in combination with a step of removing excess phenol under reduced pressure as necessary or deactivating and removing the catalyst with an adsorbent or washing with water.

The phosphate ester flame retardant produced by the above method usually contains a blend of a plurality of oligomers of an organic phosphate ester. In the general formula (1), n represents the polymerization of these oligomers. It shows the average value of degrees. In the phosphate ester flame retardant preferably used in the present invention, n is 0 to 5, more preferably n is 1 to 3, and further more preferably n is 1.
~ 2.

As the phosphate ester flame retardant used in the present invention, more specifically, the following compound No. 1 to No.
5 are mentioned.

[0036]

Embedded image (In the formula, n represents a number of 1 or more and 10 or less.)

[0037]

Embedded image (In the formula, n represents a number of 1 or more and 10 or less.)

[0038]

Embedded image (In the formula, n represents a number of 1 or more and 10 or less.)

[0039]

Embedded image (In the formula, n represents a number of 1 or more and 10 or less.)

[0040]

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The above-mentioned phosphate ester flame retardants may be used alone or in combination of two or more. The amount of the phosphoric ester-based flame retardant to be added is 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the amorphous synthetic resin (A). If the amount of the phosphate ester-based flame retardant is less than 0.5 part by weight, there is no flame retardant effect.
If it exceeds 0 parts by weight, there is a problem that the heat distortion temperature is lowered.

The (C) zirconium salt of an organic phosphate used in the present invention is represented by the following general formula (5):
Or the compound represented by (6) is preferable.

[0043]

Embedded image (In the formula, R ₆ , R ₇ and R ₈ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted.
However, R ₆ , R ₇ and R ₈ may each independently have an ether bond. R ₆ and R ₇ may be linked by an alkylene group. )

In the above general formulas (5) and (6), R
_6, the alkyl group having 1 to 20 carbon atoms represented by R ₇ and R _8, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl,
Amyl, tertiary amyl, hexyl, 2-ethylhexyl,
n-octyl, nonyl, decyl, decyl and the like;
As the alkenyl group, vinyl, 1-methylethenyl,
2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricosenyl, and the like. , Naphthyl, 2-methylphenyl (o-tolyl, cresyl), 3
-Methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl , 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl (xylyl), 2,4-dimethylphenyl, 2,5 -Dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di Tert-butylphenyl,
2,4-ditertiary pentylphenyl, 2,5-ditertiary amylphenyl, 2,5-ditertiary octylphenyl, 2,4
-Dicumylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl (mesityl) and the like. Examples of the alkylene group connecting R ₆ and R ₇ include methylene, ethylene, trimethylene, tetramethylene and the like.

The organic phosphate ester zirconium salt compound is a salt of an organic phosphate ester and zirconium metal. For example, an alkali metal salt of an organic phosphate ester is reacted with a zirconium halide or zirconium oxide halide. Thereafter, if necessary, it can be produced by a hydrolysis method or the like. Specific examples of the organophosphate zirconium salt compound include the following compound No. 6-No. 18 are mentioned.

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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Among the zirconium organic phosphate ester compounds, the acyclic organic phosphate zirconium salt compound and / or the aryl organic phosphate zirconium salt compound are preferred because of their good compatibility with the resin. The amount of the organic phosphoric acid ester zirconium salt compound to be added is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the amorphous synthetic resin (A). If the amount of the organic phosphoric acid ester zirconium salt compound is less than 0.05 part by weight, the effect as a flame retardant aid is not obtained. If it exceeds 5 parts by weight, there is a problem that the physical properties of the resin are rather reduced.

The flame-retardant synthetic resin composition of the present invention may contain a well-known general anti-drip agent in order to prevent dripping of the resin during combustion. Suitable anti-drip agents in the present invention include, for example, fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate Perfluoroalkanesulfonic acid alkali metal perfluoroalkanesulfonic acid compounds such as perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt, etc. Metal-class salts and silicone rubbers can be used, and these can be used alone or in combination of two or more.

The amount of these anti-drip agents is
(A) 0.05 parts by weight based on 100 parts by weight of the amorphous synthetic resin.
When the amount is less than 5 parts by weight, the drip prevention effect is small, and when the amount exceeds 5 parts by weight, the heat shrinkage of the molded product is increased, the dimensional accuracy may be reduced, and the cost may be increased.
5 parts by weight is preferable, and 0.1 to 2 parts by weight is more preferable.

In the case of imparting stabilization to the flame-retardant synthetic resin composition of the present invention, a general-purpose ultraviolet absorber, an antioxidant, Additives such as agents and light stabilizers can be added.

Examples of the ultraviolet absorber include, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole,
2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-
Polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2
-Hydroxy-3- (2-acryloyloxyethyl)
-5-methylphenyl] benzotriazole, 2- [2
-Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole,
2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl ] -5
Chlorobenzotriazole, 2- [2-hydroxy-5
-(2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-
Tertiary amyl-5- (2-methacryloyloxyethyl)
Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole,
2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-
Hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2
2- [2 such as-[2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole;
-Hydroxyphenyl) benzotriazoles; 2-
(2-hydroxy-4-methoxyphenyl) -4,6-
Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl ) -4,6-bis (2,4-
Dimethylphenyl) -1,3,5-triazine, 2-
[2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-
Methylphenyl) -1,3,5-triazine, 2-
(2,4-dihydroxy-3-allylphenyl) -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine, 2,4,6-tris (2-hydroxy-3
-Methyl-4-hexyloxyphenyl) -1,3,5-
2- (2-hydroxyphenyl) -4 such as triazine,
6-diaryl-1,3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,
4-di-tert-butylphenyl-3,5-di-tert-butyl-4
Benzoates such as -hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2
Substituted oxanilides such as -ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3-
Cyanoacrylates such as (p-methoxyphenyl) acrylate; various metal salts or metal chelates, particularly nickel or chromium salts or chelates.

The amount of these ultraviolet absorbers added is (A)
If the amount is less than 0.001 part by weight with respect to 100 parts by weight of the amorphous synthetic resin, a sufficient stabilizing effect cannot be obtained. Therefore, 0.001 to 10 parts by weight is preferred, and 0.0
5 to 5 parts by weight are more preferred.

Examples of the antioxidants include the following phosphorus antioxidants, phenolic antioxidants and sulfur antioxidants. Triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,
6-dimethylphenyl) .ethyl phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyldiisodecyl phosphite, tributyl phosphite, Tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexane dimethyldi Phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diste Rylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidenediphenylphosphite, bis [2,2 '-
Methylenebis (4,6-diamylphenyl)] • isopropylidenediphenylphosphite, hydrogenated-4,4'-
Isopropylidene diphenol polyphosphite, bis
(Octylphenyl) bis [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol)]
1,6-hexanediol diphosphite, tetratridecyl / 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl- 5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10-
Phosphorus antioxidants such as phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tri-tert-butylphenol monophosphite.

2,6-di-tert-butyl-p-cresol,
2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-
Di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy)
-S-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4 , 4'-butylidenebis (4,6-di-tert-butylphenol), 2,2 '
-Ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl -6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate ,
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5 -Di-tert-butyl-4
-Hydroxyphenyl) propionate] methane, 2-
Tert-butyl-4-methyl-6- (2-acryloyl-3-tert-butyl-5-methylbenzyl) phenol,
3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5. 5] Undecane] and phenolic antioxidants such as triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and β-alkylmercaptopropionate esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate) And other sulfur-based antioxidants.

When the amount of the antioxidant added is less than 0.001 part by weight based on 100 parts by weight of the amorphous synthetic resin (A), a sufficient stabilizing effect cannot be obtained, and the amount exceeds 10 parts by weight. No increase in additive effect is seen even when used with
0.001 to 10 parts by weight is preferable, and 0.05 to 10 parts by weight is more preferable.

The flame-retardant synthetic resin composition of the present invention may further contain, if necessary, other flame retardants or flame retardant auxiliaries, pigments, dyes, lubricants, antistatic agents, foaming agents, reinforcing materials, Well-known general additives such as a filler, a release agent, a fluidity improver, and an antibacterial agent can be blended at any stage such as at the time of mixing the resin and at the time of molding. Examples of the other flame retardants or flame retardant assistants include other organic phosphorus-based flame retardants, inorganic phosphorus-based flame retardants, triazine ring-containing compounds, metal hydroxides, halogen-based flame retardants, and silicon-based flame retardants. Examples of the reinforcing material include reinforcing fiber materials such as glass fiber, carbon fiber, polyamide fiber, and aromatic polyester fiber, and examples of the filler include calcium carbonate, talc, silica, carbon black, and titanium oxide. Can be

The flame-retardant synthetic resin composition of the present invention comprises
It is used for housing materials in the fields of electronic equipment, communication equipment, and OA equipment, such as copiers, printers, facsimile machines, personal computers, and the like, as alternative materials for metal products in the field of automobile parts.

[0071]

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

(Example 1 and Comparative Example 1) Polycarbonate (PC) resin (Europin E-2000F: manufactured by Mitsubishi Gas Chemical Co., Ltd.), polytetrafluoroethylene (PTFE, Teflon) were prepared according to the formulations shown in Tables 1 and 2 below. 6J:
Mitsui / Dupont Fluorochemical Co., Ltd.), phosphate ester-based flame retardant (abbreviated as phosphorus-based flame retardant in the table) and organic phosphate zirconium salt compound (abbreviated as organic zirconium phosphate in the table) 280 ° C, 250
Pellets were formed using a twin screw extruder set at rpm.
A test piece was prepared from the obtained pellet at a mold temperature of 60 ° C. using an injection molding machine at a cylinder temperature of 280 ° C., and the obtained test piece was subjected to a flame-retardant UL-94V test and measurement of an oxygen index. Was. The results are shown in Tables 1 and 2 below.

<Flame retardant UL-94V test> UL-94V
Standard: length 127mm, width 12.7mm, thickness 1.6m
After the test piece of m was held vertically and a burner fire was indirectly fired at the lower end for 10 seconds, the flame was removed and the time until the fire ignited the test piece (burning time) was measured. Next, the second flame contact was started for 10 seconds at the same time when the fire was extinguished, and the time until the ignited fire extinguished (combustion time) was measured in the same manner as in the first time. In addition, whether the cotton under the test piece ignited due to the falling fire type was also evaluated at the same time.

The burning rank was assigned according to the above-mentioned UL-94V standard from the first and second burning times, the presence or absence of cotton ignition, and the like. As for the combustion rank, V _o is the highest, and V
₁ , V ₂ , the flame retardancy decreases. Where V
which do not correspond to any of the rank _o ~V ₂ is the NR. Compliant with UL-94V combustion test (1/16 inch thickness)

[0075]

[Table 1]

[0076]

[Table 2]

(Example 2 and Comparative Example 2) Polycarbonate resin (Europin E-2000FN: manufactured by Mitsubishi Gas Chemical Co., Ltd.) was prepared according to the formulations shown in Tables 3, 4 and 5 below.
ABS resin (Santak AT-05: manufactured by Nippon A & L), polytetrafluoroethylene (Teflon 6)
J: Du Pont-Mitsui Fluorochemicals Co., Ltd.), a phosphate ester-based flame retardant and an organic phosphate ester zirconium salt compound were mixed and kneaded with a twin-screw extruder set at 260 ° C. and 250 rpm to form pellets. . The pellets were injection-molded at a set temperature of 260 ° C. and a mold temperature of 60 ° C.
The L-94V test and the measurement of the oxygen index were performed. The results are shown in Tables 3, 4 and 5 below.

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

Example 3 Poly (2,6-dimethyl-1,4-phenylene ether) and high-impact polystyrene (HIPS in the table) were prepared according to the formulations shown in Tables 6 and 7 below.
), A phosphate ester-based flame retardant and an organic phosphate ester zirconium salt compound were mixed and melt-kneaded at 280 ° C using an extruder to obtain a resin composition.
A test piece was prepared using the obtained resin composition, and a test piece was prepared in Example 1.
The flame retardancy UL-94V test was conducted in the same manner as in Example 1. The results are shown in Tables 6 and 7 below.

[0082]

[Table 6]

[0083]

[Table 7]

[0084]

Industrial Applicability The flame-retardant synthetic resin composition of the present invention is a non-crystalline synthetic resin composition having good physical properties and excellent flame retardancy, containing a phosphate ester-based flame retardant. .

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Kazuhiko Hayashi 5-2-13 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (72) Hideaki Yukitake 5-2-13-Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. BN15X BN16W CC03W CC16W CC18W CD00W CF21W CG00W CG01W CG02W CG03W CH07W CK02W CP033 EV258 EW046 EW047 FD010 FD050 FD070 FD136 FD137 FD203 FD208 GN00 GQ00

Claims (12)

[Claims] 1. (A) 100 to 100 parts by weight of an amorphous synthetic resin, (B) 0.5 to 30 parts by weight of a phosphate ester-based flame retardant represented by the following general formula (1), and (C) organic phosphorus A flame-retardant synthetic resin composition containing 0.05 to 5 parts by weight of an acid ester zirconium salt compound. Embedded image (Wherein R ₁ , R ₂ , R ₄ and R ₅ are the same or different and represent an alkyl group having 1 to 10 carbon atoms or an aromatic group represented by the following general formula (2). R ₃ Represents a divalent aromatic group represented by the following general formula (3) or (4).
Indicates 0 to 10. ) (Wherein A ₁ and A ₂ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom or an alkyl group having 1 to 10 carbon atoms, and A ₃ , A ₄ , A ₅ , A ₆ , A ₇ and A _{And 8} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a halogen atom or a cyano group. , A sulfone group, an alkylidene group having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms.) 2. The flame-retardant synthetic resin composition according to claim 1, wherein the (A) non-crystalline synthetic resin is a polycarbonate resin. 3. The flame-retardant synthetic resin composition according to claim 1, wherein the non-crystalline synthetic resin (A) is a multi-component polymer compound comprising a polycarbonate resin and a styrene resin. 4. The flame-retardant synthetic resin composition according to claim 3, wherein the styrene resin is an acrylonitrile butadiene styrene (ABS) resin. 5. The flame-retardant synthetic resin composition according to claim 1, wherein the (A) non-crystalline synthetic resin is a polyphenylene ether (PPE) resin. 6. The flame-retardant synthesis according to claim 1, wherein the (C) zirconium organic phosphate ester compound is a compound represented by the following general formula (5) or (6). Resin composition. Embedded image (In the formula, R ₆ , R ₇ and R ₈ each independently represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted.
However, R ₆ , R ₇ and R ₈ may each independently have an ether bond. R ₆ and R ₇ may be linked by an alkylene group. ) 7. The flame-retardant synthetic resin composition according to claim 1, wherein the (C) zirconium organic phosphate ester compound is a compound represented by the following chemical formula (7). Embedded image 8. The phosphoric ester-based flame retardant (B),
The flame-retardant synthetic resin composition according to claim 1 or 2, wherein in the general formula (1), n is a phosphate ester-based flame retardant having an average value of 1 to 3. 9. The (B) phosphate ester-based flame retardant,
In the above general formula (1), R ₁ , R ₂ , R ₄ and R ₅
Is an aromatic group represented by the general formula (2), and R
₃ is a divalent aromatic group represented by the general formula _{(3), A 1, A} 2, A 3 and claim 4, wherein A ₄ is a phosphate flame retardant are each hydrogen atom Flame-retardant synthetic resin composition. 10. The phosphoric ester-based flame retardant (B) is an aromatic compound represented by the general formula (1), wherein R ₁ , R ₂ , R ₄ and R ₅ are each represented by the general formula (2). R ₃ is a divalent aromatic group represented by the above general formula (3), A ₁ and A ₂ are each methyl, A ₃ and A
₄ is a phosphate flame retardant are each hydrogen atom claim 4 flame retardant synthetic resin composition. 11. The (B) phosphate ester-based flame retardant
In the general formula (1), R₁, R_Two, R_Fouras well as
R_FiveIs an aromatic group represented by the above general formula (2)
R_ThreeIs a divalent aromatic group represented by the above general formula (4)
And A₁, A _Two, A_Five, A₆, A₇And A₈Is each
A phosphoric acid salt in which B is isopropylidene
The flame-retardant synthetic resin set according to claim 4, which is a stell-based flame retardant.
Adult. 12. The flame-retardant synthetic resin according to claim 1, further comprising 0.05 to 5 parts by weight of an anti-drip agent based on 100 parts by weight of the amorphous synthetic resin (A). Composition.