JP2003082211A - Flame retardant resin composition - Google Patents

Abstract

(57) Abstract: A highly flame-retarded polyalkylene arylate-based resin composition is obtained. SOLUTION: A polyalkylene arylate-based resin is made flame-retardant using a flame retardant composed of a phosphazene compound, a polyphenylene oxide-based resin and, if necessary, a styrene-based resin and / or a nitrogen-containing compound. The phosphazene compound contains at least a crosslinked phenoxyphosphazene compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition containing a polyalkylene arylate resin, a method for producing the same, and a molded article formed from this flame-retardant resin composition.

[0002]

Polyalkylene terephthalate resins such as polybutylene terephthalate have excellent mechanical properties,
It has electrical characteristics, weather resistance, water resistance, chemical resistance and solvent resistance. Therefore, it is used as an engineering plastic for various purposes such as electric / electronic parts, machine mechanism parts, and automobile parts. On the other hand, these resins are required to be flame-retardant in terms of safety as the fields of application expand. Generally, there is known a method of making a resin flame-retardant by adding a halogen compound or a halogen-based flame retardant which is a combination of a halogen compound and an antimony compound to a resin. However, in halogen-based flame retardants,
A large amount of dioxin compounds may be generated during combustion decomposition, which is environmentally unfavorable. Therefore, a method of making a polyester resin flame-retardant by using a phosphorus compound as a non-halogen flame retardant has been proposed.

Japanese Unexamined Patent Publication (Kokai) No. 10-168297 discloses a flame-retardant resin composition comprising a thermoplastic polyester resin, a polycarbonate resin, and a phosphate-based organic phosphorus flame retardant. Japanese Patent Laid-Open No. 10-195283
In the publication, a phosphoric acid ester having a specific structure, a novolac-type phenol resin, and an appropriate amount of an oxide of a specific metal such as iron, cobalt, nickel, or copper are flame-retarded to make a polyester resin composition flame-retarded. It is disclosed.
Japanese Unexamined Patent Publication No. 2000-212412 discloses a flame-retardant resin composition comprising a thermoplastic polyester resin, a vinyl resin, an organic phosphorus flame retardant (condensed phosphate ester, etc.), and glass fiber. However, although the phosphoric acid ester-based flame retardant does not contain harmful halogen, it is inferior in flame retardancy to the halogen-based flame retardant, and thus requires a large amount of flame retardant. Therefore, bleed-out and deterioration of the mechanical properties of the resin are caused, and the flame retardancy and mechanical properties cannot be improved.

Further, in JP-A No. 11-181268, 100 parts by weight of a resin containing an aromatic polycarbonate resin and a thermoplastic polyester resin at 90/10 to 50/50 (weight ratio) is used. It is disclosed that the resin mixture can be flame-retarded by adding 1.5 to 15 parts by weight of the phosphazene compound and 0.5 to 30 parts by weight of talc and / or mica. However, the aromatic polycarbonate-based resin composition has a problem in solvent resistance, and also has poor melt flowability during molding, resulting in poor moldability.

In JP-A-11-181429, a specific phosphazene compound (a cyclic phosphazene compound, a linear phosphazene compound, a crosslinked phosphazene compound obtained by crosslinking the cyclic and / or linear phosphazene compound with a specific group) is disclosed. Etc.) as a flame retardant to flame-retard either a thermoplastic resin (polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc.) or a thermosetting resin (phenolic resin, etc.).
However, when flame retarding polyethylene terephthalate or polybutylene terephthalate, the phosphazene compound alone is insufficient in flame retardancy.

[0006]

Therefore, an object of the present invention is to provide a highly flame-retarded resin composition and a method for producing the same, without deteriorating the characteristics of the polyalkylene arylate resin. .

[0007] Another object of the present invention is to provide a resin composition and a molded article which are suppressed in exudation of a flame retardant, do not cause metal corrosion, have excellent moldability, and have high flame retardancy. It is in.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned objects, and as a result, if at least a phosphazene compound and a polyphenylene oxide resin are combined to form a flame retardant, the mechanical properties are deteriorated. It was found that the polyalkylene arylate resin can be made highly flame-retardant without being involved, and that the bleed-out of the flame retardant from the molded product, metal corrosion, and the moldability during injection molding can be greatly improved. Completed the invention.

That is, the flame-retardant resin composition of the present invention is
A composition comprising a flame retardant and a polyalkylene arylate resin (polyethylene terephthalate resin, polybutylene terephthalate resin, etc.), wherein the flame retardant comprises a specific phosphazene compound and a polyphenylene oxide resin. ing. The phosphazene compound contains at least the following crosslinked phenoxyphosphazene compound.

Crosslinked phenoxyphosphazene compound Formula (1)

[0011]

[Chemical 4]

(In the formula, m represents an integer of 3 to 25. Ph
Represents a phenyl group) and a cyclic phenoxyphosphazene compound represented by the formula (2)

[0013]

[Chemical 5]

[Wherein X ¹ represents a group -N = P (OPh) ₃ or a group -N = P (O) OPh, and Y ¹ represents a group -P (OPh) ₄ or a group -P (O) ( OPh) ₂ is shown. n represents an integer of 3 to 10,000. Ph is the same as the above formula (1)], and at least one phenoxyphosphazene compound selected from the chain-like phenoxyphosphazene compounds represented by o-
Phenylene group, m-phenylene group, p-phenylene group and formula (3)

[0015]

[Chemical 6]

[In the formula, A is --C (CH ₃ ) _2- , --SO
_2- , -S- or -O- is shown. a represents 0 or 1]
At least 1 selected from the bisphenylene groups represented by
A compound cross-linked with a cross-linking group of two species, the cross-linking group being interposed between two oxygen atoms from which the phenyl group of the phosphazene compound has been eliminated, and the content of the phenyl group in the cross-linking compound is Phosphazene compounds (1) and (2)
A compound which is 50 to 99.9 mol% based on the total number of all phenyl groups in at least one phosphazene compound selected from and does not have a free hydroxyl group in the molecule.

The phosphazene compound may further contain the cyclic phenoxyphosphazene compound (1), the chain phenoxyphosphazene compound (2) and the like.

The proportion of the polyphenylene oxide resin in the flame retardant may be about 10 to 500 parts by weight with respect to 100 parts by weight of the phosphazene compound. The flame retardant may further be composed of a styrene resin, a nitrogen-containing compound or the like. The proportion of the flame retardant is about 5 to 300 parts by weight with respect to 100 parts by weight of the polyalkylene arylate resin. The flame retardant may further be composed of a phosphorus compound, a carbonizing resin, an inorganic metal compound, or the like. The resin composition of the present invention may further contain an antioxidant, an anti-dripping agent, a release agent, a filler and the like.

The present invention also includes a method for producing a flame-retardant resin composition by mixing the flame retardant and a polyalkylene arylate resin. The present invention also includes a molded product formed from the composition.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION [Polyalkylene arylate-based resin] Examples of the polyalkylene arylate-based resin include alkylene arylate (eg, alkylene terephthalate).
As a main component (for example, 50 to 100% by weight, preferably 7
5 to 100% by weight) homopolyester or copolyester. Homopolyesters include, for example, poly 1,4-cyclohexane dimethylene terephthalate (PCT), polyethylene terephthalate (PE
T), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polypropylene naphthalate (P
PN), polybutylene naphthalate (PBN) and the like. Copolyester copolymerizable monomers include (poly) ethylene glycol, (poly) trimethylene glycol, (poly) propylene glycol, (poly) butylene glycol, 1,6-hexanediol,
Alcohol components such as 1,4-cyclohexanedimethanol, aliphatic dicarboxylic acids (adipic acid, sebacic acid, decanedicarboxylic acid, etc.), aromatic dicarboxylic acids (isophthalic acid, naphthalenedicarboxylic acid, biphenylenedicarboxylic acid, etc.), hydroxycarboxylic acid Carboxylic acid components such as acids (hydroxybenzoic acid, hydroxynaphthoic acid, etc.), phenol components such as hydroquinone, resorcinol, biphenol, alkylene oxide adducts of dihydric phenol components [bis (2-hydroxyethoxy) benzene, bis [4- (2-hydroxyethoxy)
And a dihydroxy component such as phenyl] propane. These polyalkylene arylate resins can be used alone or in combination of two or more.

Preferred polyalkylene arylate resins are polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, and the like. In particular, poly C _2-4 alkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, isophthalate. A copolyester such as a polybutylene terephthalate / isophthalate copolymer having an acid as a copolymerization component (such as a poly C _2-4 alkylene terephthalate / isophthalate copolymer) is preferable.

The number average molecular weight of the polyalkylene arylate resin is not particularly limited and is, for example, 5 × 10 ³ to 10 ^3.
It can be selected from the range of 0 × 10 ⁴ , preferably 1 × 10 ⁴ to 70 × 10 ⁴ , and more preferably 1.2 × 10 ⁴ to 30 × 10 ⁴ .

The polyalkylene arylate resin can be prepared by a conventional method, for example, alkylene glycol and an aromatic dicarboxylic acid or its ester (for example, terephthalic acid or dimethyl terephthalate, isophthalic acid or dimethyl isophthalate as a copolymerization component). It can be produced by a direct esterification method using and or a transesterification reaction.

[Flame Retardant] The flame retardant of the present invention comprises a specific phosphazene compound and a polyphenylene oxide resin. The flame retardant may be composed of a phosphazene compound, a polyphenylene oxide resin, and optionally a styrene resin and / or a nitrogen-containing compound. When such a flame retardant is used, the polyalkylene arylate resin can be made highly flame retardant without deterioration in mechanical properties. Furthermore, the present invention does not particularly require a compatibilizer,
It is possible to suppress deterioration of mechanical properties.

(Phosphazene Compound) The phosphazene compound includes a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound, a crosslinked phenoxyphosphazene compound and the like. In the present invention, the phosphazene compound contains at least a crosslinked phenoxyphosphazene compound.

Examples of the cyclic phenoxyphosphazene compound include compounds represented by the following formula (1).

[0027]

[Chemical 7]

(In the formula, m represents an integer of 3 to 25. Ph
Represents a phenyl group).

The chain phenoxyphosphazene compound includes compounds represented by the following formula (2).

[0030]

[Chemical 8]

[Wherein X ¹ represents a group -N = P (OPh) ₃ or a group -N = P (O) OPh, and Y ¹ represents a group -P (OPh) ₄ or a group -P (O) ( OPh) ₂ is shown. n represents an integer of 3 to 10,000. Ph is the same as the above formula (1)].

The crosslinked phosphazene compound is a compound obtained by crosslinking at least one phenoxyphosphazene compound selected from the cyclic phenoxyphosphazene compound (1) and the chain phenoxyphosphazene compound (2) with a divalent crosslinking group. Can be mentioned. Incidentally, in the case of crosslinking a set of phenoxyphosphazene compounds with the crosslinking group,
A divalent bridging group is introduced in place of the pair of Ph groups.

The divalent bridging group includes a phenylene group (o-phenylene group, m-phenylene group, p-phenylene group),
A bisphenylene group represented by the following formula (3) is included. In addition, these crosslinking groups can be used individually or in combination of 2 or more types.

[0034]

[Chemical 9]

[In the formula, A is --C (CH ₃ ) _2- , --SO
_2- , -S- or -O- is shown. a represents 0 or 1.].

The proportion of phenyl groups in the crosslinked phenoxyphosphazene compound is 50 to 9 based on the total number of all phenyl groups in the phosphazene compound (1) and / or (2).
It is about 9.9 mol%.

The crosslinked phenoxyphosphazene compound has substantially no free (free) hydroxyl group in the molecule.

Cyclic and linear phenoxyphosphazene compounds represented by the formulas (1) and (2) are, for example, HRAllc.
ock, “Phosphorus-Nitrogen Compounds”, Academic
Press, (1972), JEMark, HRAllcock, R. West,
“Inorganic Polymers”, Prentice-Hall Internationa
l, Inc., (1992) and the like.

For example, phosphorus chloride (phosphorus trichloride, phosphorus pentachloride, etc.), ammonium chloride, and optionally chlorine (especially when phosphorus trichloride is used as phosphorus chloride) in a chlorine-based solvent (chlorobenzene). , Tetrachloroethane, etc.), the OPh group of the formula (1) is substituted with a chlorine atom (Cl), and m is a compound represented by an integer of 3 to 25 (cyclic dichlorophosphazene oligomer); A mixture with the compound (chain dichlorophosphazene oligomer) in which the OPh group of (2) is substituted with a chlorine atom and n is an integer of 3 to 25 is obtained. The chlorine atom of this dichlorophosphazene oligomer mixture is
By substituting phenol with an alkali metal phenolate (such as sodium phenolate), cyclic and chain phenoxyphosphazene compounds represented by the formulas (1) and (2) can be obtained.

The reaction temperature of phosphorus chloride and ammonium chloride is, for example, about 120 to 130 ° C.

The dichlorophosphazene oligomer mixture may be purified (distillation, recrystallization, etc.) or polymerized (ring-opening polymerization of cyclic dichlorophosphazene oligomer), if necessary. By purifying the dichlorophosphazene oligomer mixture, a single substance of cyclic dichlorophosphazene (hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, etc.) can be taken out. Therefore, by substituting this single substance with phenol, a cyclic phenoxyphosphazene compound such as hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaffenoxycyclopentaphosphazene, or the like can be obtained.

On the other hand, ring-opening polymerization of the cyclic dichlorophosphazene oligomer gives a compound in which the OPh group of the formula (2) is substituted with a chlorine atom and n is an integer of 3 to 10,000. Therefore, by substituting this compound with phenol, a chain phenoxyphosphazene compound represented by the formula (2) can be obtained.

Ring-opening polymerization of the cyclic dichlorophosphazene oligomer can be carried out, for example, by heating at 220 to 250 ° C.

The crosslinked phenoxyphosphazene compound is a diphenylphosphazene compound (1) or a chain phosphazene compound (2). It can be produced by substituting (crosslinking) some chlorine atoms with an alkali metal salt of an aromatic dihydroxy compound.

The dichlorophosphazene oligomer may be a mixture of a cyclic dichlorophosphazene oligomer and a linear dichlorophosphazene oligomer, or may be separated and used alone. The alkali metal salt of phenol and the alkali metal salt of aromatic dihydroxy compound may be mixed for reaction, or may be reacted with the alkali metal salt of phenol and then reacted with the alkali metal salt of aromatic dihydroxy compound. Alternatively, the reaction may be performed in the reverse order.

More preferably, the dichlorophosphazene compound (such as a cyclic dichlorophosphazene oligomer or a chain dichlorophosphazene oligomer) is reacted with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound (first Reaction of the second step), among the chlorine atoms of the dichlorophosphazene compound,
Partially substituted with phenol, partly substituted with aromatic dihydroxy compound, and partly obtained with partially substituted chlorine compounds remaining as chlorine atoms. Then, the crosslinked phenoxyphosphazene compound can be obtained by reacting the partially substituted product with an alkali metal salt of phenol (second reaction). In the thus-obtained crosslinked phenoxyphosphazene compound, all the hydroxyl groups of the aromatic dihydroxy compound have reacted with the dichlorophosphazene compound, so that free (free) hydroxyl groups do not substantially remain.

The aromatic dihydroxy compound is a compound having one or two or more benzene rings in the molecule and two hydroxyl groups, more specifically, the above-mentioned bridging group (o-phenylene group, A compound having an m-phenylene group, a p-phenylene group, a group represented by the formula (3) can be used. Preferred aromatic dihydroxy compounds include resorcinol, hydroquinone, catechol, bis (4-hydroxyphenyl) alkanes such as bisphenols [4,4'-isopropylidene diphenol (bisphenol-A), 4,4'-sulfonyldiphenol. (Bisphenol-S), 4,4'-thiodiphenol, 4,4'-oxydiphenol, 4,4'-diphenol, etc.] and the like. The aromatic dihydroxy compounds can be used alone or in combination of two or more.

Examples of the alkali metal constituting the alkali metal salt include sodium, potassium and lithium, preferably sodium and lithium.

In the first-step reaction, the total amount of the alkali metal salt of phenol and the alkali metal salt of aromatic dihydroxy compound used is generally 0.05 to 0.05 based on the chlorine amount of the dichlorophosphazene oligomer. 0.
It is about 9 equivalents, preferably about 0.1 to 0.8 equivalents. If the amount of the alkali metal salt used is significantly smaller than 0.05 equivalent, the degree of crosslinking will be insufficient. On the other hand, when the amount used is much larger than 0.9 equivalent, a free (free) hydroxyl group (one end hydroxyl group of the dihydroxy compound) is introduced into the crosslinked phenoxyphosphazene compound.

The ratio of the alkali metal salt of the aromatic dihydroxy compound and the alkali metal salt of phenol is not particularly limited and can be appropriately selected from a wide range. Usually, the former / the latter =
It is about 1/2000 to 1/4 (molar ratio). When the ratio is significantly smaller than 1/2000, the degree of crosslinking is insufficient. On the other hand, when the ratio is much larger than 1/4, the crosslinking proceeds too much, the solubility or the melting property of the crosslinked phenoxyphosphazene compound is lowered, and the dispersibility in the resin becomes insufficient.

The first-step reaction may be carried out in a solvent (aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as chlorobenzene).

The reaction temperature in the first step is usually from room temperature to 15
It is about 0 ° C.

In the second stage reaction, the amount of the alkali metal salt of phenol used is usually about 1 to 1.5 equivalents based on the amount of chlorine of the dichlorophosphazene oligomer.
It is preferably about 1 to 1.2 equivalents.

The chlorine content of the phosphazene compound is 2000 ppm or less (for example, 0 to 2) in the phosphazene compound.
000 ppm), preferably 0 to 1500 ppm, more preferably 0 to 1000 ppm.

The proportion of the phosphazene compound in the flame-retardant resin composition is, for example, 1-40% by weight, preferably 1-3.
It is 0% by weight, more preferably about 5 to 25% by weight. The ratio of the phosphazene compound is 0.1 to 1 with respect to 100 parts by weight of the polyalkylene arylate resin.
The amount is 00 parts by weight, preferably 1 to 80 parts by weight, more preferably 5 to 70 parts by weight. If the ratio of the phosphazene compound to the polyalkylene arylate-based resin is too large, the mechanical properties of the resin composition deteriorate.

(Polyphenylene oxide resin) Polyf
Enylene oxide resin (polyphenylene ether resin)
The fat) includes a homopolymer and a copolymer. Alone
The polymer may be poly (2,6-dimethyl-1,4-phenyl).
(Elenylene) oxide, poly (2,5-dimethyl-1,4)
-Phenylene) oxide, poly (2,5-diethyl-)
1,4-phenylene) oxide, poly (2-methyl-6)
-Ethyl-1,4-phenylene) oxide, poly (2,2
6-di-n-propyl-1,4-phenylene) oxy
De, poly (2-ethyl-6-isopropyl-1,4-phenyl)
Enylene) oxide, poly (2-methyl-6-methoxy)
-1,4-phenylene) oxide, poly (2-methyl-)
6-hydroxyethyl-1,4-phenylene) oxy
De, poly (2-methyl-6-chloroethyl-1,4-phenyl)
(Elenylene) oxide, poly (2,3,6-trimethyl-
1,4-phenylene) oxide and other poly (mono, di or
Is a bird C_1-6Alkyl-phenylene) oxide, poly
(2-Methyl-6-phenyl-1,4-phenylene) o
Poly (mono C_1-6Alkyl-mono C_6-10A
Reel-phenylene) oxide, poly (2,6-diphene)
Poly (mono) such as nyl-1,4-phenylene) oxide
Or the C _6-10Aryl-phenylene) oxide, etc.
You can

As the copolymer of polyphenylene oxide, a copolymer having two or more monomer units of the above homopolymer (for example, 2,6-dimethyl-1,4-phenylene oxide units and 2,3,6- Trimethyl-1,4
-A random copolymer having a phenylene oxide unit), a benzene formaldehyde resin (formaldehyde condensation product of a benzene ring-containing compound such as a phenol resin) or an alkylbenzene formaldehyde resin is reacted with an alkylphenol such as cresol or p-tert-butylphenol. A modified polyphenylene oxide copolymer composed of an alkylphenol-modified benzene-formaldehyde resin block obtained as described above and a polyphenylene oxide block as a main structure, a polyphenylene oxide or a copolymer thereof is grafted with a styrene compound and / or an acid anhydride. And modified graft copolymers.

The intrinsic viscosity of the polyphenylene oxide resin is a value measured at 30 ° C. in chloroform, preferably 0.2 to 0.8 dl / g, more preferably 0.25 to 0.25.
It is about 0.7 dl / g.

These polyphenylene oxide resins are
You may use it individually or in combination of 2 or more types.

The proportion of polyphenylene oxide resin is
10 to 50 relative to 100 parts by weight of the phosphazene compound
The amount is 0 parts by weight, preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight. The ratio of the polyphenylene oxide resin is 0.1 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 5 to 100 parts by weight of the polyalkylene arylate resin.
It is about 70 parts by weight. When the ratio of the polyphenylene oxide resin to the polyalkylene arylate resin is too large, the mechanical properties of the resin composition deteriorate.

(Styrene Resin) As the styrene resin, at least one selected from homo- or copolymers of aromatic vinyl monomers, aromatic vinyl monomers, vinyl cyanide monomers and rubber components. And a copolymer composed of a seed (for example, a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, a polymer in which an aromatic vinyl monomer is graft-copolymerized with a rubber component, a rubber component). In addition, a non-crystalline rubber-like polymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are graft-copolymerized) is used.

Aromatic vinyl monomers include styrene, alkylstyrenes (for example, vinyltoluenes such as o-, m-, p-methylstyrene, vinylxylenes such as 2,4-dimethylstyrene, ethylstyrene). , P-
Alkyl-substituted styrenes such as isopropyl styrene, butyl styrene, pt-butyl styrene), α-alkyl substituted styrenes (eg, α-methyl styrene, α-ethyl styrene, α-methyl-p-methyl styrene, etc.)
Etc. can be illustrated. These styrenic monomers can be used alone or in combination of two or more. Of these styrene-based monomers, styrene, vinyltoluene, α-methylstyrene and the like, particularly styrene, are preferable.

As the vinyl cyanide monomer, for example,
Examples thereof include (meth) acrylonitrile. Vinyl cyanide monomers may be used alone or in combination of two or more. The preferred vinyl cyanide monomer is acrylonitrile.

As the rubber component, conjugated diene rubber (polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, etc.), olefin Examples of the rubber include ethylene-propylene rubber (EPDM rubber), ethylene-vinyl acetate copolymer, halogenated polyolefin (chlorinated polyethylene, etc.), acrylic rubber, etc. Even if these rubber components are hydrogenated products. Good. These rubber components are
They can be used alone or in combination of two or more. Among these rubber components, conjugated diene rubber is preferable. In the rubber component such as the conjugated diene rubber, the gel content is not limited at all. Further, the rubber component can be produced by a method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, solution-bulk polymerization, bulk-suspension polymerization and the like.

Aromatic vinyl monomers may also be incorporated into other copolymers.
A compatible monomer may be used in combination. As a copolymerizable monomer
Is, for example, a (meth) acrylic acid ester [eg,
Methyl (meth) acrylate, Ethyl (meth) acrylate
L, butyl (meth) acrylate, (meth) acrylic acid t
-Butyl, hexyl (meth) acrylate, (meth) ac
Octyl acrylate, 2-ethylhexyl (meth) acrylate
(Meth) acrylic acid C such as _1-18Alkyl ester,
2-Hydroxyethyl (meth) acrylate, (meth) a
Containing hydroxyl group such as 2-hydroxypropyl acrylate
Existence (meth) acrylate, glycidyl (meth) acryl
Etc.], a carboxyl group-containing monomer [for example ((
Unsaturated monocarboxylic acid such as acrylic acid and crotonic acid
Acid, maleic anhydride, maleic acid, fumaric acid, itacone
Aliphatic unsaturated dicarboxylic acid such as acid, maleic acid monoester
Tell (monomethyl maleate, monoethyl maleate,
Maleic acid mono C such as monobutyl maleate_1-10Archi
Ester) and the corresponding fumaric acid monoesters
Unsaturated dicarboxylic acid monoesters such as], Murray
Mido-based monomers [eg, maleimide, N-methyl maleide
N-alkylmaleimides such as amide, N-phenylmale
Imide and the like]. These copolymerizable monomers
Can be used alone or in combination of two or more. Preferred
(Meth) acrylic acid ester as the copolymerizable monomer
(Especially methylmethacrylate), (meth) acrylic acid,
Maleic anhydride, a maleimide type monomer, etc. are contained.

When a vinyl cyanide monomer is used, the ratio (weight ratio) of the aromatic vinyl monomer and the vinyl cyanide monomer is, for example, aromatic vinyl monomer / vinyl cyanide monomer. Body = 10/90 to 90/10, preferably 2
It is about 0/80 to 80/20.

When the rubber component is used, the ratio (weight ratio) of the rubber component and the aromatic vinyl monomer is 5 / 95-80 / 20, preferably 10 / rubber component / aromatic vinyl monomer.
It is about / 90 to 70/30. If the proportion of the rubber component is too small, the impact resistance of the resin composition will be lowered, and if it is too large, the dispersion will be poor and the appearance will be easily deteriorated.

When another copolymerizable monomer is used, the ratio (weight ratio) of the aromatic vinyl monomer to the other polymerizable monomer
Is an aromatic vinyl monomer / other copolymerizable monomer = 100
/ 0 to 10/90, preferably 90/10 to 10/9
0, and more preferably about 80/20 to 20/80.

Preferred styrene resins include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), and high impact polystyrene (HIP).
S), graft polymer [acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile] -Ethylene-propylene rubber-styrene copolymer (AES resin), acrylonitrile-butadiene rubber-methyl methacrylate-styrene copolymer (ABSM resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), etc.],
Block copolymer [eg, styrene-butadiene-styrene (SBS) copolymer, styrene-isoprene-styrene (SIS) copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, etc.), styrene-acrylonitrile -Ethylene-propylene-ethylidene norbornene copolymer (AES) and the like], or hydrogenated products thereof. Particularly preferred styrene resins include polystyrene (GPPS), styrene-ethylene-butylene-styrene (SEBS) copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin).
Etc. are included. These styrene resins can be used alone or in combination of two or more.

The proportion of the styrene resin is 0 to 100 parts by weight (for example, 0.1 to 100 parts by weight), preferably 1 to 70 parts by weight, more preferably 5 to 50 parts by weight based on 100 parts by weight of the phosphazene compound. It is about part by weight. The ratio of the styrene resin is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight, and more preferably 5 to 100 parts by weight of the polyalkylene arylate resin.
It is about 30 parts by weight. If the ratio of the styrene-based resin to the polyalkylene arylate-based resin is too large, the mechanical properties of the resin composition deteriorate.

(Nitrogen-Containing Compound) The nitrogen-containing compound is preferably a nitrogen-containing cyclic compound, for example, a salt of a nitrogen-containing cyclic compound having an amino group and cyanuric acid or a derivative thereof, and a nitrogen-containing cyclic compound having an amino group. Salts of oxyacids, salts of nitrogen-containing cyclic compounds having amino groups and organic phosphonic acids or organic phosphinic acids [eg nitrilotris (methylphosphonate) mono- or hexamelamine salts, 1-hydroxyethylidene-1,1-] Diphosphonic acid mono- or tetramelamine salt and the like; melam salt corresponding to the melamine salt, melem salt, melamine-melam-melem double salt and the like], urea compound (eg, acetylene urea, cyclic urea compound such as uric acid), polyphosphoric acid Examples include amides. Among these, the salt (a) of the nitrogen-containing cyclic compound having an amino group and cyanuric acid or a derivative thereof, and the salt (b) of the nitrogen-containing cyclic compound having an amino group and an oxygen acid are particularly preferable.

As the nitrogen-containing cyclic compound having an amino group as the component (a), amino group-containing triazines, particularly 1,3,5-triazines, are preferable, and examples thereof include melamine and melamine condensates (melam, melem, melon). Etc.) and guanamines (guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipguanamine, etc.) can be exemplified. As cyanuric acid or a derivative thereof, cyanuric acid, isocyanuric acid,
Ammeline and ammelide can be exemplified. Specifically, as the salt (a) of a nitrogen-containing cyclic compound having an amino group and cyanuric acid, a melamine salt of cyanuric acid such as melamine cyanurate, a melam salt of cyanuric acid, a melem salt of cyanuric acid, and a cyanuric acid Guanamine salts and the like can be mentioned. A nitrogen-containing cyclic compound having an amino group,
The ratio with cyanuric acid or its derivative is not particularly limited, but for example, the former / latter (molar ratio) = 1/2 to 3 /
1, preferably about 1/1 to 2/1.

Examples of the nitrogen-containing cyclic compound having an amino group that can be used in the component (b) include the same nitrogen-containing cyclic compounds as those in the component (a). Generally, the nitrogen-containing cyclic compound having an amino group preferably forms a salt with at least one amino group substituted on the ring and an oxygen acid. When it has a plurality of amino groups, all the amino groups may form a salt with an oxygen acid. Further, a plurality of the same or different nitrogen-containing compounds (the nitrogen-containing cyclic compound and other amino group-containing nitrogen-containing compounds) may form a salt with one polyacid to form a double salt of the polyacid. . Examples of the oxygen acid include phosphoric acid (non-condensed phosphoric acid, condensed phosphoric acid, etc.), sulfuric acid (non-condensed sulfuric acid such as peroxomonosulfuric acid, sulfuric acid; condensed sulfuric acid such as peroxodisulfuric acid, pyrosulfuric acid), boric acid (non-condensed acid). Condensed boric acid, condensed boric acid, etc.) and the like. Of these oxygen acids, phosphoric acids (phosphoric acid; triphosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc.) and sulfuric acid are preferable. Specifically,
Examples of the component (b) include melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melem polyphosphate, melamine / melam / melem polyphosphate double salt, melamine sulfate, melam sulfate, melem sulfate, melamine melam sulfate.・ Melem double salt and the like can be mentioned.

These nitrogen-containing compounds can be used alone or in combination of two or more.

The proportion of the nitrogen-containing compound is 0 to 300 parts by weight (eg, 5 to 300 parts by weight), preferably 10 to 200 parts by weight, and more preferably 20 to 150 parts by weight, relative to 100 parts by weight of the phosphazene compound. It is a degree.
The ratio of the nitrogen-containing compound is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polyalkylene arylate resin.
It is about part by weight. If the ratio of the nitrogen-containing compound to the polyalkylene arylate-based resin is too large, the mechanical properties of the resin composition deteriorate.

Since the flame retardant of the present invention contains a polyphenylene oxide resin, the polyalkylene arylate resin has a molecular weight and mechanical properties (strength, impact resistance, etc.).
It is possible to make the polyalkylene arylate resin flame-retardant while suppressing the decrease of In particular, when the phosphazene compound is used in combination with the polyphenylene oxide resin and, if necessary, in combination with the styrene resin and / or the nitrogen-containing compound, the polyalkylene arylate resin is highly advanced as compared with the case of using the phosphazene compound alone. Can be flame retardant. In addition, since the flame retardant does not contain halogen, there is no risk of generating hydrogen halide which is a toxic gas when decomposing or burning, and the resin is not corroded or the resin is corroded with resin molding. There is no risk of deterioration.

The proportion of the flame retardant (the total of the phosphazene compound, the polyphenylene oxide resin, the styrene resin, and the nitrogen-containing compound) in the resin composition is not particularly limited as long as the characteristics of the polyalkylene arylate resin are not impaired. The flame retardant is 5 to 300 parts by weight, preferably 10 to 20 parts with respect to 100 parts by weight of the polyalkylene arylate resin.
The amount is 0 parts by weight, more preferably about 20 to 150 parts by weight. If the proportion of the flame retardant is too small, flame retardation is difficult, and if it is too large, the mechanical strength and moldability of the molded product obtained from the resin composition are reduced.

The polyalkylene arylate-based resin composition of the present invention contains other flame-retardant agents, if desired, such as phosphorus compounds, carbonizing resins, inorganic metal compounds, silicon compounds (zeolites, (branched) silicones). Resins, silicone oils, etc.), sulfur compounds (alkyl or aromatic sulfonic acid metal salts, perfluoroalkyl sulfonic acid metal salts, salts of alkanesulfonic acid with amino group-containing triazines, etc.)], additives (eg, Anti-dripping agent, antioxidant, release agent, etc.) may be included.

[Other Flame Retardants] Other flame retardants include phosphorus compounds, carbonizing resins, inorganic metal compounds and the like.
Other flame retardants can be used alone or in combination of two or more.

(Phosphorus Compound) The phosphorus compound includes an organic phosphorus compound and an inorganic phosphorus compound. As the organic phosphorus compound, an aromatic phosphorus compound is preferable, and examples thereof include aromatic phosphate esters (tricresyl phosphate, trixylyl phosphate, etc.), condensed aromatic phosphate esters [hydroquinone bis (diphenyl phosphate), hydroquinone bis ( Resorcinol bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dixylyl phosphate) and other resorcinol phosphates; biphenol bis (diphenyl phosphate), biphenol bis (dicresyl) Phosphate), biphenol phosphates such as biphenol bis (dixylyl phosphate); bisphenol-A bis (diphenyl phosphate), bis Bisphenol-A phosphates such as enol-A bis (dicresyl phosphate), bisphenol-A bis (dixylyl phosphate); phloroglucinol tris (diphenyl phosphate), phloroglucinol tris (dicresyl phosphate), phloroglucinol tris (Dixylyl phosphate) and other phloroglucinol phosphates], aromatic phosphinic acid esters (9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide and the like).

Further, as another preferable organic phosphorus compound,
And organic phosphinic acid metal salt [di-C _1-6Alkyl phosph
Phosphoric acid, C_1-6Alkyl C_6-10Arylphosphinic acid,
The C_{6- Ten}Metal salts such as arylphosphinic acid (Mg, C
a, Ba, Zn, polyvalent metal salts such as Al salts), etc.]
You can

Examples of the inorganic phosphorus compound include red phosphorus (stabilized red phosphorus, etc.) which may be coated with a resin, a metal component, etc., and polyphosphate (polyphosphoric acid, which may be coated with a resin, a metal component, etc.). Ammonium, etc., (sub) phosphoric acid metal salts (such as calcium phosphate and other alkaline earth metal salts), hydrogen phosphate metal salts (such as calcium hydrogen orthophosphate and alkaline earth metal salts), etc. To be

These phosphorus compounds can be used alone or in combination of two or more.

(Carbonizing Resin) Examples of the carbonizing resin include resins having an aromatic ring. Such aromatic ring resins include phenolic resins (for example, novolac resins,
Examples thereof include aralkyl resin, polyvinylphenol resin, etc., polycarbonate resin, polyarylate resin, aromatic epoxy resin (eg, phenoxy resin), polyphenylene sulfide resin, polyetherimide resin and the like. These carbonizing resins can be used alone or in combination of two or more.

(1) Phenolic resin (1-1) Novolac resin Examples of novolac resins include phenols [phenol,
C_1-20(Preferably C _1-10) An alkyl-substituted phen
Noles (eg cresol, xylenol, ethyl phen
Enol, propylphenol, butylphenol, o
(Cutylphenol, nonylphenol, etc.), cyanophene
Nols, arylphenols (eg phenylpheno)
, Benzylphenol, cumylphenol, etc.), etc.]
And aldehydes (formaldehyde, acetaldehyde
And aliphatic aldehydes such as propionaldehyde, benzene
Aromatic aromatic compounds such as zaldehyde and phenylacetaldehyde
Obtained from reaction with aldehydes, especially formaldehyde)
Phenol novolac resin is used. Feno
Lunovolac resins include, for example, phenolic hydroxide.
Random group with random methylene bonds to the group
For novolak resin and phenolic hydroxyl group
High ortho novolac tree with many methylene bonds at the luso position
Examples include fats (for example, resins with an ortho / para ratio of 1 or more)
it can. Of these phenolic novolac resins, the balance
Monomer-less resins and dimers with reduced distillate phenols
-Less resin is preferred. Also, phenol novolac tree
Fats include aminotriazines (eg, melamine, guar).
Namin, acetoguanamine, benzoguanamine, etc.)
Aminotriazine-modified phenol modified or copolymerized
Also includes novolac resins. These novolac resins
Can be used alone or in combination of two or more.

(1-2) Aralkyl Resin As the aralkyl resin, aralkyl resins such as p-
Xylylene glycol, p-xylylene glycol C
_1-4 alkyl ethers (p-xylylene glycol dimethyl ether, p-xylylene glycol diethyl ether, etc.), acyloxyaralkyls (p-xylylene-α, α′-diacetate, etc.), aralkyldiols (p-xylylene-α, etc.) , Α′-diol, etc.), aralkyl halides (p-xylylene-α, α′-dichloride, p-xylylene-α, α′-dibromide, etc.), etc.]
And a phenol aralkyl resin obtained by the reaction with a phenol (eg, the phenol or alkylphenol exemplified in the section of the novolak resin), JP-A-2000-351.
The aralkyl resin described in Japanese Patent No. 822, etc. may be mentioned. These aralkyl resins can be used alone or in combination of two or more kinds.

Phenol aralkyl resins are commercially available under the trade names "Mirex" (manufactured by Mitsui Chemicals, Inc.), "Sumilite Resin PR-54443" (manufactured by Sumitomo Durres Co., Ltd.), and "X".
ylok "(Albright & Wilson Corporation)
Manufactured by Meiwa Kasei Co., Ltd.).

(1-3) Polyvinylphenol Resin As the polyvinylphenol resin, a homopolymer of an aromatic vinyl monomer having a hydroxyl group (for example, vinylphenol, dihydroxystyrene, etc.), the aromatic vinyl monomer and other Copolymerizable monomer [eg,
Styrenes such as styrene, vinyltoluene, α-methylstyrene; (meth) acrylic acid, (meth) acrylic acid such as (meth) acrylic acid or derivatives thereof (ester, acid amide, etc.), (meth) acrylonitrile, etc.] And the like.

The ratio (weight ratio) of the vinyl monomer and the copolymerizable monomer is, for example, 10/90 to 100/0, preferably 30/70 to 100/0, more preferably 4
0/60 to 100/0 (especially 50/50 to 100/0)
It is a degree. Preferred polyvinylphenols are vinylphenol homopolymers (polyhydroxystyrene), especially p-vinylphenol homopolymer.

In the phenolic resin, some or all of the phenolic hydroxyl groups are glycidyl ether groups,
Modified phenolic resins converted to functional groups such as acyl groups (acetyl groups, etc.), aroyl (benzoyl groups, toluoyl groups, etc.), alkyl ether groups, aryl ether groups, or (phosphite), (phosphite) Also included are phosphorus compounds such as esters, boric acid, and modified phenolic resins modified with inorganic metal salts.

The number average molecular weight of the phenolic resin is
Without limitation, for example, 300 to 50 × 10^Four, Preferably
Is 400 to 30 × 10^FourAnd more preferably 500 to 5
× 10 ^FourYou can choose from a range of degrees.

(2) Polycarbonate Resin Polycarbonate resin contains a dihydroxy compound and
Included are polymers obtained by reaction with carbonic acid esters such as phosgene or diphenyl carbonate. Dihydroxy compounds include bisphenol compounds [eg, bisphenol A, bisphenol F, bisphenol AD
Bis (hydroxyaryl) C _1-6 alkane; bis (hydroxyaryl) C _4-10 cycloalkane;
4'-dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl ketone, etc.], alicyclic compounds (for example, 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A) and the like. At least one of the dihydroxy compound and the carbonic acid ester is an aromatic compound.

The number average molecular weight of the polycarbonate resin is not particularly limited, and may be, for example, 300 to 50 × 10 ⁴ ,
Preferably 400 to 30 × 10 ⁴ , more preferably 5
It can be selected from the range of about 00 to 5 × 10 ⁴ .

(3) Polyarylate Resin The polyarylate resin can be obtained by reacting an aromatic polyol component and a polycarboxylic acid component (such as an aromatic polycarboxylic acid component). The polycarboxylic acid component is
Usually, it contains at least an aromatic polycarboxylic acid component.

Examples of aromatic polyols include benzenediols (resorcinol, hydroquinone, xylylene glycol, etc.), bisphenols such as biphenol, bis (hydroxyaryl) C _1-6 alkane (eg, bisphenol A, bisphenol F, bisphenol). AD etc.) etc. are included.

Examples of the aromatic polycarboxylic acid component include monocyclic aromatic dicarboxylic acids (particularly benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid),
Examples thereof include bis (carboxyaryl) C _1-6 alkane.

Preferred polyarylate resins are polyarylate resins in which the aromatic polyol is a bisphenol, such as bisphenols (biphenol, bisphenol A, bisphenol AD, bisphenol F).
Etc.) with benzenedicarboxylic acid (isophthalic acid, terephthalic acid, etc.), bisphenols and bis (arylcarboxylic acids) [eg, bis (carboxyphenyl) methane, bis (carboxyphenyl) ethane, bis (carboxyphenyl) Examples thereof include polyesters with bis (carboxyaryl) C _1-4 alkyl such as propane.

The polyarylate resin may form a polymer alloy with a resin other than the polyarylate resin, for example, a polyester resin (PET or the like), a polycarbonate resin, a polyamide resin, or the like.

The number average molecular weight of the polyarylate resin is
For example, 300 to 30 × 10 ⁴ , preferably 500 to 1
It is 0 × 10 ⁴ , more preferably about 500 to 5 × 10 ⁴ .

(4) Aromatic Epoxy Resins Aromatic epoxy resins include glycidyl ether type epoxy resins (eg, biphenol type epoxy resin, bisphenol type epoxy resin, novolac type epoxy resin, etc.), glycidyl ester type epoxy resin, aromatic. A glycidyl amine epoxy resin using an amine component is included.

As the bisphenol type epoxy resin,
For example, bis (hydroxyaryl) C _1-6 alkane,
Particularly, glycidyl ethers such as bisphenol A, bisphenol AD, bisphenol F and the like can be mentioned. Also,
Examples of the bisphenol type epoxy resin include the above-mentioned bisphenol glycidyl ether having a large molecular weight (that is, phenoxy resin). Examples of the novolac type epoxy resin include an alkyl group (for example, C
Examples thereof include glycidyl ethers of novolac resins (eg, phenol novolac resins and cresol novolac resins) which may be substituted with _1-20 alkyl groups, preferably C _1-4 alkyl groups such as methyl group and ethyl group.

The number average molecular weight of the aromatic epoxy resin is, for example, 200 to 50,000, preferably 300 to 1
It is about 10,000, more preferably about 400 to 6,000 (for example, 400 to 5,000). The number average molecular weight of the phenoxy resin is, for example, 500 to 50,0.
00, preferably 1,000 to 40,000, and more preferably about 3,000 to 35,000.

(Inorganic Metal Compound) Examples of the inorganic metal compound include metal hydroxides (eg magnesium hydroxide,
Aluminum hydroxide, etc.), metal borate (eg, hydrous zinc borate, hydrous calcium borate, etc.), stannic acid metal salt (eg, hydrous zinc stannate, etc.), metal sulfate, metal oxide (eg, oxidation) Molybdenum, tungsten oxide,
Antimony oxide, zirconium oxide, etc.), metal sulfides (eg, zinc sulfide, molybdenum sulfide, tungsten sulfide, etc.) and the like. These inorganic metal compounds can be used alone or in combination of two or more.

The proportion of the other flame retardant is 0 to 100 parts by weight, preferably 0 to 80 parts by weight, and more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyalkylene arylate resin.
It is about 60 parts by weight.

[Additives] As additives, antioxidants,
It includes heat stabilizers, anti-dripping agents, mold release agents, fillers and the like. The additives may be used alone or in combination of two or more.

(Antioxidant) As the antioxidant, a hindered phenolic antioxidant [2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-t) is used. -Butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,
4'-thiobis (6-t-butyl-m-cresol),
Branched C _3-6 alkylphenols such as pentaerythritol-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate)], amine antioxidants (naphthylamine, phenylnaphthylamine, 1, Hindered amines such as 4-phenylenediamine), phosphorus-based antioxidants [phosphites (for example, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di- t-
Butyl (4-methylphenyl) pentaerythritol diphosphite and other bis (C _1-9 alkyl-aryl) pentaerythritol diphosphite), phosphonite (eg, tetrakis (2,4-di-t-butylphenyl)) -4,4'-biphenylenediphosphonite, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, etc.)] and the like. These antioxidants can be used alone or in combination of two or more.

(Heat Stabilizer) Examples of the heat stabilizer include inorganic phosphorus stabilizers such as phosphoric acid, phosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, acidic phosphoric acid alkali metal salts (sodium dihydrogen phosphate, etc.), Examples thereof include alkaline earth metal salts of acidic phosphates (such as calcium dihydrogen phosphate and calcium dihydrogen pyrophosphate). These heat stabilizers can be used alone or in combination of two or more kinds.

(Dripping prevention agent) As the dripping prevention agent, a fluorine-based resin such as a homopolymer or copolymer of a fluorine-containing monomer, a copolymer of a fluorine-containing monomer and another copolymerizable monomer, or a layered silica. Examples thereof include acid salts. As such a fluorine-based resin, specifically, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer Examples thereof include polymers, ethylene-tetrafluoroethylene copolymers and ethylene-chlorotrifluoroethylene copolymers. These anti-dripping agents can be used alone or in combination of two or more kinds.

(Release Agent) As the release agent, waxes (for example, C _1-4 olefin wax such as polyethylene wax, ethylene copolymer wax, polypropylene wax, etc.), higher fatty acid salts (for example, C ₈ Higher fatty acid metal salts such as _-35 fatty acid alkali metal salts), higher fatty acid esters (eg higher fatty acid alkyl esters such as C _8-35 fatty acid alkyl esters), higher fatty acid amides (eg C _8-35 fatty acid amides, Examples thereof include alkylene bis fatty acid amides) and silicone compounds (eg, silicone oil, silicone resin). These release agents can be used alone or in combination of two or more kinds.

(Filler) As the filler, fibrous fillers (glass fiber, carbon fiber, etc.), powdery fillers (silicates such as kaolin and talc; metal carbonates such as calcium carbonate; titanium oxide) Etc.), plate-like fillers (mica, glass flakes, various metal foils, etc.), and the like. Among these fillers, fibrous fillers, particularly glass fibers (chopped strands) are preferable because they have high strength and rigidity. These fillers can be used alone or in combination of two or more.

These fillers may be used in combination with a sizing agent or a surface treatment agent. As such a sizing agent or surface treatment agent, a functional compound is included. Examples of the functional compound include epoxy compounds, silane compounds, titanate compounds, and the like.

The resin composition of the present invention may further contain other additives, such as nucleating agents, lubricants, plasticizers, flame retardant aids, stabilizers (ultraviolet absorbers, heat stabilizers), if necessary. It may contain colorants (pigments, dyes), antistatic agents, dispersants, antibacterial agents and the like.

The proportion of each additive is, for example, 0.01 to 100 parts by weight of the polyalkylene arylate resin.
20 parts by weight, preferably about 0.01 to 10 parts by weight. Further, among the additives, the filler is 5 to 60% by weight, preferably 5 to 50% by weight in the flame-retardant resin composition.
% By weight, more preferably 5 to 45% by weight (especially 5 to 4%
0% by weight).

[Method for Producing Flame Retardant Resin Composition] The resin composition of the present invention may be a mixture of powder and granules, a melt mixture, a polyalkylene arylate resin, a flame retardant and, if necessary, an additive. It can be prepared by mixing and with a conventional method.

The resin composition of the present invention can be melt-kneaded and molded by a conventional method such as extrusion molding, injection molding or compression molding. Since the formed article has excellent flame retardancy and molding processability, it can be used for various purposes. For example, it can be suitably used for electric / electronic parts, machine mechanism parts, automobile parts and the like.

[0116]

In the present invention, since a flame retardant obtained by combining a specific phosphazene compound, a polyphenylene oxide resin, and optionally a styrene resin and / or a nitrogen-containing compound is used, it is possible to use a halogen-based flame retardant without using It is possible to make the polyalkylene arylate resin flame-retardant.
Particularly, in the present invention, the properties of the flame-retarded polyalkylene arylate-based resin are not deteriorated, and the polyalkylene arylate-based resin can be highly flame-retarded. Furthermore, by using a specific phosphazene, the moldability (mold deposit), the exudation of the flame retardant from the molded product, and the metal corrosiveness are significantly improved.

[0117]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

In Examples and Comparative Examples, the flame retardancy of resin compositions was evaluated by the following tests. In addition, the following polyester resins, flame retardants (phosphazene compounds, polyphenylene oxide resins, styrene resins, nitrogen-containing compounds), and, if necessary, other flame retardants (phosphorus compounds, carbonizing resins, inorganic metal compounds) ), Additives (antioxidants, heat stabilizers, anti-dripping agents, release agents) and fillers.

[Flammability test] According to UL94, the flammability was evaluated with a test piece having a thickness of 1.6 mm.

[Evaluation of seepage of flame retardant (blooming property)] A flame-retardant evaluation test piece was put in a gear oven and set to 1
After standing still at 50 ° C. for 10 hours, the surface of the molded piece was visually observed to evaluate the exudation (blooming) state in the following 5 stages.

[0121] A: None B: There is a little C: Yes D: Many E: Very many.

[Metal Corrosion] 100 g of the extruded pellet composition and a silver plate (1 × 1 cm) were placed in a 500 ml glass stopper bottle, and the bottle was stoppered and allowed to stand at 120 ° C. for 72 hours. Was visually observed and evaluated according to the following criteria.

[0123] A: No change B: There is corrosion.

[Moldability (Amount of Die Deposit)] Pellets formed of the flame-retardant composition and molded into a specific shape (diameter 20).
mm × thickness 1 mm) was continuously molded (500 shots) using a 30t injection molding machine, and the degree of mold deposit (mold deposit) was evaluated in 5 levels. It should be noted that the smaller the value is, the less the amount of deposits on the mold, that is, the less the mold deposit.

[Polyalkylene terephthalate A] A-1: Polybutylene terephthalate [Duranex, intrinsic viscosity = 1.0, manufactured by Polyplastics Co., Ltd.] A-2: Polybutylene terephthalate [Duranex, intrinsic viscosity = 0] .75, Polyplastics Co., Ltd.
Made] A-3: Polyethylene terephthalate [Belpet EF
G10, manufactured by Kanebo Co., Ltd.] A-4: Polybutylene terephthalate copolymer in which 12.5 mol% of terephthalic acid is replaced with isophthalic acid [intrinsic viscosity = 1.0].

[Phosphazene Compound B] B-1 to B-3: Bridged phenoxyphosphazene compound B'-1 obtained by the following Synthesis Examples 1 to 3: Cyclic phosphazene compound (hexachlorocyclotriphosphazene and phenol in tetrahydrofuran, After reacting in the presence of triethylamine, the reaction solution was concentrated under reduced pressure, and the residue was washed with water to obtain a phosphazene compound), and a chlorine content of 2000 ppm or more.

[Polyphenylene Oxide Resin C] C-1: Poly (2,6-dimethyl-1,4-phenylene) oxide [PPE polymer YPX-100F, manufactured by Mitsubishi Gas Chemical Co., Inc.].

[Styrene Resin D] D-1: Polystyrene [Toyostyrol GP G2
00C, manufactured by Toyo Styrene Co., Ltd.] D-2: Acrylonitrile-styrene copolymer [Diapet AS AP-10, manufactured by Mitsubishi Rayon Co., Ltd.].

[Nitrogen-containing compound E] E-1: Melamine cyanurate [MC610, manufactured by Nissan Chemical Industries, Ltd.] E-2: Melamine polyphosphate [PMP100, manufactured by Nissan Chemical Industries, Ltd.] E-3: Polyphosphorus Acid melam [PMP200, manufactured by Nissan Chemical Industries, Ltd.].

[Other Flame Retardant F] (Carbonating Resin F1) F1-1: Polycarbonate [Panlite L1225,
Teijin Chemicals Ltd.] F1-2: Polyarylate [Polyarylate U Polymer U8400, Unitika Ltd.] F1-3: Bisphenol-A type epoxy resin [Epicoat 1004K, Yuka Shell Epoxy Ltd.] F1 -4: Phenol novolac type epoxy resin [EP
PN, manufactured by Nippon Kayaku Co., Ltd.] F1-5: Bisphenol-A type epoxy resin [Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.].

(Inorganic metal compound F2) F2-1: Magnesium hydroxide [Kisuma 5E, manufactured by Kyowa Chemical Industry Co., Ltd.] F2-2: Hydrous zinc borate [Fire Brake Z]
B, US Borax Co., Ltd.] F2-3: hydrous calcium borate [UB powder, Kinse Tech Co., Ltd.] F2-4: anhydrous phosphoric acid-calcium hydrogen [manufactured by Taihei Chemical Industry Co., Ltd.].

(Phosphorus compound F3) F3-1: Resorcinol bis (di-2,6-xylyl phosphate) [PX200, manufactured by Daihachi Chemical Industry Co., Ltd.] F3-2: ethylmethylphosphinic acid aluminum salt.

[Antioxidant / Thermal Stabilizer G] G-1: Pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] [Irganox 1010, manufactured by Ciba Geigy] G-2: Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite [Adeka Stab PEP36, manufactured by ADEKA ARGUS] G-3: Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite [Sand Stub P-EPQ, manufactured by Sand Co.] G-4: Calcium dihydrogen phosphate .

[Dripping prevention agent H] H-1: polytetrafluoroethylene.

[Release agent I] I-1: Pentaerythritol tetrastearate [Unistar, manufactured by NOF CORPORATION] I-2: Montanate ester [LUZA WAX, manufactured by Toyo Petrolite Co., Ltd.] I-3 : Polyethylene wax [Sun wax, manufactured by Sanyo Chemical Industry Co., Ltd.].

[Filler J] J-1: Glass fiber [chopped strand having a diameter of 10 μm and length of 3 mm] J-2: Glass fiber [chopped strand having a diameter of 13 μm and length of 3 mm] J-3: Talc [talc 3A Manufactured by Nippon Talc Co., Ltd.].

Synthesis Example 1 (Synthesis of phenoxyphosphazene compound (B-1) having a crosslinked structure with 4,4'-sulfonyldiphenylene (bisphenol-S residue)) 0.4 mol of phenol (37.6 g) and THF500
To a 1-liter four-necked flask containing mL, 0.4 g atom (9.2 g) of metallic sodium that had been finely chopped was charged while maintaining the internal temperature at 25 ° C. with stirring. After completion of the addition, stirring was continued for 5 hours at 65 to 72 ° C. until the metallic sodium completely disappeared.

In parallel with the above reaction, tetrahydrofuran (THF) 5 of 1.70 mol (160.0 g) of phenol and 0.05 mol (12.5 g) of bisphenol-S was added.
In a 1 liter four-necked flask containing the 00 mL solution,
1.8 grams of sodium metal (41.
4 g) was added. After charging, the temperature was raised to 61 ° C. over 1 hour, and stirring was continued at 61 to 68 ° C. for 6 hours to prepare a sodium phenolate mixed solution. This solution was added to dichlorophosphazene oligomer (trimer 62% by weight, tetramer 1
2 wt%, pentamer and hexamer 11 wt%, heptamer 3 wt%, mixture of octamer and 12 wt%) 20 wt% chlorobenzene solution containing 1.0 unit mol (115.9 g) While stirring, the mixture was added dropwise to 580 g while being cooled to 25 ° C or lower, and the mixture was stirred and reacted at 71 to 73 ° C for 5 hours. Next, the previously prepared sodium phenolate mixed solution was added dropwise, and the reaction was continued at 71 to 73 ° C. for 3 hours.

After completion of the reaction, the reaction mixture was concentrated, redissolved in 500 mL of chlorobenzene, washed with 5 wt% NaOH water three times, washed with 5 wt% sulfuric acid, washed with 5 wt% sodium bicarbonate water, and washed with water. Was repeated 3 times, and the mixture was concentrated to dryness to obtain 218 g of a pale yellow wax.

Crosslinked phenoxyphosphase obtained above
The hydrolyzed chlorine of the phosphorus compound is 0.01% by weight or less,
From the phosphorus content and CHN elemental analysis value, the composition of this product
Is approximately [N = P (-O-Ph-SO₂-Ph-O-)
_0.05(-O-Ph)_1.90] Was decided. Weight average molecular weight
(Mw) is 1080 in terms of polystyrene, and TG /
The melting temperature by DTA analysis is 103 ℃, the decomposition start temperature is
The temperature at 320 ° C. and the 5% weight loss was 334 ° C. Well
Quantification of residual hydroxyl groups by the acetylation method
As a result, the detection limit (hydroxyl / g sample was
As equivalent weight: 1 x 10 ^-6Equivalent / g or less) or less
It was

Synthesis Example 2 (Synthesis of phenoxyphosphazene compound (B-2) having a crosslinked structure with metaphenylene) 1.1 mol (103.5 g) of phenol and 1.1 mol (44.0 g) of sodium hydroxide A mixture of 50 g of water and 500 mL of toluene was heated under reflux, and only water was removed to the outside of the system to prepare a toluene solution of sodium phenolate.

In parallel with the above reaction, in a 2 liter four-necked flask, 0.15 mol (16.5 g) resorcinol, 1.0 mol (94.1 g) phenol, 1.3 mol (31.1 g). A mixture of lithium hydroxide of 5), water (52 g) and toluene (600 mL) was heated under reflux to remove only water out of the system to prepare a toluene solution of a lithium salt of resorcinol and phenol. Dichlorophosphazene oligomers (62% by weight of trimer, 12% by weight of tetramer, 11% by weight of pentamer and 11% by weight of hexamer, 3% by weight of 7mer, 8% by weight) of this toluene solution were stirred at 30 ° C or lower. More than 1
2% by weight of mixture) 1.0 unit mol (115.9)
580 g of a 20 wt% chlorobenzene solution containing g) was added dropwise, and the mixture was reacted at 110 ° C. for 3 hours with stirring. The toluene solution of sodium phenolate was added to the reaction mixture, and the reaction was continued at 110 ° C. for 4 hours.

After completion of the reaction, the reaction mixture was washed 3 times with 1.0 L of a 3% by weight aqueous sodium hydroxide solution, and then with water 1.
After washing 3 times with 0 L, the organic layer was concentrated under reduced pressure. The obtained product was heated and vacuum dried at 80 ° C. and 400 Pa or less for 11 hours to obtain 209 g of a white powder.

The hydrolyzed chlorine of the obtained crosslinked phenoxyphosphazene compound was 0.08% by weight, and the weight average molecular weight (Mw) was 1 in terms of polystyrene (by GPC analysis).
The composition of the final product was [N = (-O-m-Ph-O-) from the phosphorus content and CHN elemental analysis value.
_0.15 (-O-Ph) _1.7 ]. TG / DTA analysis does not show a clear melting point, decomposition onset temperature is 304 ° C, 5%
The weight loss temperature was 311 ° C. In addition, as a result of quantifying the residual hydroxyl group by the acetylation method, it was found that the detection limit (hydroxy equivalent per 1 g of the sample: 1
^{X10 -6} equivalent / g or less) or less.

Synthesis Example 3 (Synthesis of phenoxyphosphazene compound (B-3) having a crosslinked structure with 2,2-bis (p-oxyphenyl) isopropylidene group) 0.7 mol of phenol (65.9 g) and 50 of toluene
In a 1 liter four-necked flask containing 0 mL, with stirring,
While keeping the internal liquid temperature at 25 ° C., 0.65 gram atom (14.9 g) of metal sodium finely cut was added. After the addition, stirring was continued at 77 to 113 ° C. for 8 hours until the metallic sodium completely disappeared.

In parallel with the above reaction, bisphenol-A
0.25 mol (57.1 g), phenol 1.1 mol (103.5 g) and tetrahydrofuran (THF) 8
Into a 3 liter four-necked flask containing 00 mL, 1.6 g atom (11.1 g) of finely chopped metallic lithium was charged with stirring while maintaining the internal liquid temperature at 25 ° C. or lower. After the addition, stirring was continued for 8 hours at 61 to 68 ° C. until the metallic lithium completely disappeared. This slurry solution was stirred and the internal liquid temperature was kept at 20 ° C. or lower while dichlorophosphazene oligomer (concentration: 37 wt%, chlorobenzene solution 313 g, composition: trimer 75 wt%, 4
17% by weight of monomer, 6% by weight of pentamer and 6% by weight of hexamer, 1 of 7
1.0 wt% (mixture of octamer and 1 wt% or more) 1.0 unit mol (115.9 g) was added dropwise over 1 hour and reacted at 80 ° C. for 2 hours. Next, while stirring, while maintaining the internal liquid temperature at 20 ° C., the separately prepared sodium phenolate solution was added over 1 hour, and the reaction was carried out at 80 ° C. for 5 hours.

After completion of the reaction, the reaction mixture was concentrated to give THF.
Was removed, and 1 L of toluene was newly added. The toluene solution was washed 3 times with 1 L of a 2 wt% NaOH aqueous solution and then with 1.0 L of water 3 times, and then the organic layer was concentrated under reduced pressure. The obtained product was heated and vacuum dried at 80 ° C. and 400 Pa or less for 11 hours to obtain 229 g of a white powder.

The hydrolyzed chlorine of the crosslinked phenoxyphosphazene compound obtained above was 0.07% by weight, and the composition of the final product was [N = P
(-O-Ph-C (CH 3) 2 -Ph-O-) 0.25 (-O-P
h) _1.50 ]. The weight average molecular weight (Mw) is 1130 in terms of polystyrene (by GPC analysis), and T
G / DTA analysis showed no clear melting point, and the decomposition initiation temperature was 308 ° C and the 5% weight loss temperature was 313 ° C. Moreover, as a result of quantifying the residual hydroxyl group by the acetylation method, it was below the detection limit (hydroxy equivalent per 1 g of the sample: 1 × 10 ⁻⁶ equivalent / g or less).

Examples 1 to 16 and Comparative Examples 1 to 10 In addition to polyalkylene terephthalate A, phosphazene compound B, polyphenylene oxide resin C, styrene resin D, nitrogen-containing compound E, other flame retardant F, antioxidant /
A heat stabilizer G, an anti-dripping agent H, a release agent I, a filler J, etc. are mixed in a ratio shown in Tables 1 to 3 and a 30 mmφ twin-screw extruder [TEX30, manufactured by Japan Steel Works, Ltd.] 28
The composition was obtained by kneading at 0 ° C. This polyalkylene terephthalate resin composition was injection-molded with a 50t molding machine to prepare a molded article for a combustion test, and the flammability was evaluated based on UL94 with a test piece thickness of 1.6 mm. Further, the exudation of flame retardant, metal corrosion and moldability were evaluated. The results are shown in Tables 1 to 3.

[0150]

[Table 1]

[0151]

[Table 2]

[0152]

[Table 3]

As is clear from Tables 1 to 3, the polyalkylene terephthalates of the examples are highly flame retarded.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 85/02 C08L 85/02 101/02 101/02 (72) Inventor Shinya Yamada 973 Miyajima, Fuji City, Shizuoka Prefecture Address: Polyplastix Co., Ltd. (72) Inventor Yuji Tada 463, Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Tokushima Institute Co., Ltd. AE17 BA01 BC07 4J002 BC033 BC063 BN143 CC044 CD034 CE004 CF041 CF051 CF061 CF164 CG004 CH072 CQ012 DH026 DH036 FD132 FD136

Claims (11)

[Claims] 1. A composition comprising a flame retardant and a polyalkylene arylate resin, wherein the flame retardant comprises a phosphazene compound and a polyphenylene oxide resin, and the phosphazene compound is at least the following crosslinked phenoxyphosphazene: A flame-retardant resin composition containing a compound. Crosslinked phenoxyphosphazene compound formula (1) (In the formula, m represents an integer of 3 to 25. Ph represents a phenyl group) and a cyclic phenoxyphosphazene compound represented by the formula (2) [Wherein, X ¹ is a group —N═P (OPh) ₃ or a group —N═P (O))
OPh is shown, and Y ¹ is a group —P (OPh) ₄ or a group —P (O).
(OPh) ₂ is shown. n represents an integer of 3 to 10,000. Ph is the same as the above formula (1)], at least one phenoxyphosphazene compound selected from the chain phenoxyphosphazene compounds represented by the formula (1) is an o-phenylene group, m-phenylene group, p-phenylene group and a formula (3) [Chemical Formula 3] [In the formula, A _{-C (CH 3) 2 -,} - SO 2 -, - shows S- or -O-. a represents 0 or 1] and is a compound crosslinked with at least one kind of bridging group selected from bisphenylene groups, and the bridging groups are two groups in which the phenyl group of the phosphazene compound is eliminated. Of the phenyl groups in the cross-linking compound, which is present between the oxygen atoms of 50, based on the total number of phenyl groups in at least one phosphazene compound selected from the phosphazene compounds (1) and (2). To 99.9 mol% and does not have a free hydroxyl group in the molecule 2. The composition according to claim 1, wherein the phosphazene compound further contains at least one selected from a cyclic phenoxyphosphazene compound (1) and a chain phenoxyphosphazene compound (2). 3. The composition according to claim 1, wherein the polyalkylene arylate resin is composed of at least one selected from polyethylene terephthalate resin and polybutylene terephthalate resin. 4. The composition according to claim 1, wherein the proportion of the flame retardant is 5 to 300 parts by weight based on 100 parts by weight of the polyalkylene arylate resin. 5. The composition according to claim 1, wherein the flame retardant further comprises at least one component selected from styrene resins and nitrogen-containing compounds. 6. The flame retardant is a polyphenylene oxide resin 10 to 5 relative to 100 parts by weight of the phosphazene compound.
The composition according to claim 1, which is composed of 00 parts by weight, 0 to 100 parts by weight of a styrene resin, and 0 to 300 parts by weight of a nitrogen-containing compound. 7. The composition according to claim 1, wherein the flame retardant further comprises at least one component selected from phosphorus compounds, carbonizing resins, and inorganic metal compounds. 8. The composition according to claim 1, further comprising at least one selected from an antioxidant, an anti-dripping agent, a release agent and a filler. 9. A composition comprising a flame retardant and a polyalkylene terephthalate resin, wherein 1 flame retardant is added to 100 parts by weight of the polyalkylene terephthalate resin.
0 to 200 parts by weight, the flame retardant is composed of the phosphazene compound, the polyphenylene oxide resin and the nitrogen-containing compound according to claim 1, and 30 to 100 parts by weight of the phosphazene compound is used. 300 parts by weight, styrene resin 0.1-100
A flame-retardant resin composition comprising 5 parts by weight and a nitrogen-containing compound of 5 to 300 parts by weight. 10. A method for producing a flame retardant resin composition by mixing the flame retardant according to claim 1 and a polyalkylene arylate resin. 11. A molded body formed from the composition according to claim 1.