JPH10130510A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

(57) [Abstract] [Problem] It has good flame retardancy and small variation,
Further, a thermoplastic resin composition having a small decrease in mechanical strength typified by tensile strength and flame-retarded with red phosphorus is obtained. SOLUTION: (B) Red phosphorus having a particle size of 15 to 45 μm ≧ 50% Red phosphorus having a particle size of less than 15 μm ≦ 25% Red phosphorus exceeding a particle size of 45 μm with respect to 100 parts by weight of a thermoplastic resin ≦ 25% A flame-retardant thermoplastic resin composition comprising 0.1 to 15 parts by weight of a total of 100% (all in number%) of red phosphorus satisfying ≧ 90% of red phosphorus having a particle size of 70 μm or less. .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition, and more particularly to a thermoplastic resin composition flame-retarded by red phosphorus compounds, wherein the dispersion of flame retardancy is small. The present invention belongs to the technical field of producing and using a flame-retardant thermoplastic resin composition with a small decrease in mechanical properties such as tensile strength.

[0002]

2. Description of the Related Art Thermoplastic resins represented by polycarbonate resins, polyester resins, polyolefin resins, polyamide resins, polystyrene resins, polyphenylene ether resins, thermoplastic elastomers, etc.
Since it is easy to mold, it is widely used as a material for electric / electronic parts, a material for automobile parts, a material for construction, a material for fiber, and the like.

[0003] These thermoplastic resins are properly used depending on the required characteristics of the application. However, since all of the thermoplastic resins are flammable, they are used in applications where flame retardancy is required. Improvement is a common issue.

As a technique for making a thermoplastic resin flame-retardant,
A method of adding a flame retardant is generally used. Examples of the flame retardant to be used include organic halogen compounds such as brominated epoxy resin and brominated polystyrene resin, organic phosphorus compounds such as triphenyl phosphate, and inorganic phosphorus such as red phosphorus. Examples thereof include hydrated metal compounds such as phosphorus compounds, aluminum hydroxide, and magnesium hydroxide.

[0005] In recent years, non-halogen flame retardants have been focused on organic phosphorus compounds, inorganic phosphorus compounds, hydrated metal compounds, and the like. Since it has a plasticizing effect on the thermoplastic resin, there is a problem that the mechanical strength and the heat resistance of the thermoplastic resin are reduced. On the other hand, in the case of a hydrated metal compound, it is necessary to add a relatively large amount in order to reach a target flame retardancy level, and there is a problem that the mechanical strength of the resin is reduced. For this reason,
Attention is being focused on inorganic phosphorus compounds, particularly red phosphorus.

The so-called red phosphorus compounds include, in addition to ordinary red phosphorus, JP-A-51-105996, JP-A-7-53779, JP-A-63-69704, There is a stabilized red phosphorus coated with a thermosetting resin, electroless plating or the like, which is mentioned in, for example, Japanese Patent Application Laid-Open No. 63-134507. Further, compositions flame-retarded using such stabilized red phosphorus include, for example, JP-A-48-85642, JP-A-50-78651, JP-A-63-95266, JP-A-5-23
No. 9260, and the like.

[0007] Red phosphorus is generally particles having a size of several hundred µm or less. For example, JP-A-63-110254 discloses that
A resin composition using stabilized red phosphorus having a particle size of 200 μm or less is mentioned. However, when such red phosphorus is added to the resin to form a molded body by, for example, injection molding, there is a problem that the surface is uneven, and the appearance is impaired due to red spots. Such a problem is due to the fact that particles having a relatively large particle size are mixed in the red phosphorus used, and in order to improve such a problem, Japanese Patent Application Laid-Open No. 5-295164 discloses a particle diameter of 25%.
a method of adding red phosphorus having a red phosphorus content of 10 μm or less (% by weight, hereinafter the same) or less;
No. 9 and JP-A-1-187710,
A method for adding red phosphorus of 0 μm or less is described.

[0008]

When red phosphorus having a small particle size is uniformly dispersed in a resin, the problem of appearance is certainly improved, but the thermoplastic resin has a small particle size. When red phosphoruss are added and kneaded using an extruder to obtain a composition, for example, the bulk density of the red phosphoruss is small, or secondary aggregation of the red phosphoruss causes heat. A new problem that red phosphorus is not uniformly dispersed in the plastic resin newly occurs, and on the contrary, a problem such as a decrease or variation in flame retardancy and a decrease in mechanical strength occur. all right.

[0009]

Means for Solving the Problems The present inventors have proposed a flame retardant method using red phosphorus which has good flame retardancy, small variation, and a small decrease in mechanical strength represented by tensile strength. As a result of intensive studies to obtain a modified thermoplastic resin composition, they have found that the above problem can be solved by using red phosphorus having a specific particle size distribution, and completed the present invention. I came to.

That is, the present invention relates to (A) 100 parts (parts by weight, hereinafter the same) of a thermoplastic resin, (B) red phosphorus having a particle size of 15 to 45 μm ≧ 50%, and (1) a particle size of less than 15 μm. Red phosphorus ≤ 25% (2) Red phosphorus exceeding a particle size of 45 µm ≤ 25% (3) Red phosphorus having a particle size of 70 µm or less ≥ 90% (4) Total 100% satisfying The flame-retardant thermoplastic resin composition (Claim 1), which is obtained by adding 0.1 to 15 parts of red phosphorus (hereinafter referred to as "number%"), has an oxygen atom in the molecular chain. 2. The composition according to claim 1, which contains at least 20% (% by weight, the same applies hereinafter) of a thermoplastic resin containing: a thermoplastic resin containing an oxygen atom in a molecular chain, a polycarbonate resin, or a polyester. Resin, polyamide resin, polyphenylene ether resin At least one member selected from a composition of claim 2 (claim 3), the thermoplastic resin (A)
For 100 parts, (C) fluororesin and / or silicones
The composition (Claim 4) according to any one of claims 1 to 3, wherein the composition (D) is 0.5 to 100 parts with respect to 100 parts of the thermoplastic resin (A). The composition according to any one of claims 1, 2, 3 and 4, wherein the thermoplastic resin (A) is a polycarbonate resin and / or a polyester resin. The composition according to claim 3, 4 or 5, wherein the red phosphorus is coated with at least one selected from thermosetting resin, metal hydroxide, and metal formed by plating. Claims 1 and 2 which are red phosphorus.
A composition according to claim 3, 4, 5 or 6 (claim 7).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin (A), which is the component (A) used in the present invention, is a component used as a base resin of the composition of the present invention. What is called.

Specific examples of such a thermoplastic resin (A) include a polycarbonate resin (PC resin), a polyester resin, and a polyphenylene ether resin (PP
E resin), polyamide resin, polystyrene resin,
Polyolefin resin, poly (meth) acrylate resin, polyphenylene sulfide resin, polyacetal resin, polysulfone resin, polyacetal resin,
Examples include olefin-based, polyester-based, styrene-based, and polyamide-based thermoplastic elastomers. Among these, a thermoplastic resin containing an oxygen atom in the molecular chain is preferred from the viewpoint of flame retardancy. The term “in the molecular chain” as used herein refers to a molecular end in a molecular main chain, a molecular side chain, or a molecular end, and the phrase “containing an oxygen atom in a molecular chain” means any of a molecular main chain, a molecular side chain, and a molecular end. Means that an oxygen atom is incorporated at one or more sites. Specific examples thereof include, for example, an ether bond, an ester bond, a carbonate bond,
Amide bond, urethane bond, carbonyl group, ketone group,
Examples include bonds or groups such as isocyanate groups and hydroxyl groups. Specific examples of the thermoplastic resin containing an oxygen atom in its molecular chain include thermoplastic resins such as PC-based resins, polyester-based resins, polyamide-based resins, PPE-based resins, polyacetal-based resins, polyester-based and polyamide-based thermoplastic elastomers, and acrylic resins. Examples thereof include a polyolefin resin or a thermoplastic elastomer obtained by copolymerizing an acid alkyl ester or the like. Among them, a thermoplastic resin containing an oxygen atom in a molecular main chain such as a PC resin, a polyester resin, a polyamide resin, and a PPE resin is preferable, and a PC resin and a polyester resin are particularly preferable. The thermoplastic resin (A) may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable to contain 20% or more, more preferably 50% or more of a thermoplastic resin containing an oxygen atom in a molecular chain from the viewpoint of flame retardancy.

The PC resin is, for example, a thermoplastic resin obtained by reacting a phenolic compound having a valency of 2 or more with a carbonic diester such as phosgene or diphenyl carbonate. This resin is used in fields that require properties such as heat deformation resistance and mechanical strength.

There are various kinds of the above-mentioned phenolic compounds having two or more valences. In particular, 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), which is a divalent phenol compound, is economical and mechanical. It is suitable in terms of strength. Examples of dihydric phenol compounds other than bisphenol A include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
Phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) (4-isopropylphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, bis (3,5-dimethyl) -4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-
1,1-bis (4-hydroxyphenyl) ethane, 1-
Phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-
(Hydroxyphenyl) propane, 1-ethyl-1,1-
Bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2 -Bis (3-chloro-4
-Hydroxyphenyl) propane, 2,2-bis (3-
Methyl-4-hydroxyphenyl) propane, 2,2-
Bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane, 1,
4-bis (4-hydroxyphenyl) butane, 2,2-
Bis (4-hydroxyphenyl) pentane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane, 1,
10-bis (4-hydroxyphenyl) decane, 1,1
Dihydroxydiarylalkanes such as -bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Kind;
Dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) cyclodecane Dihydroxydiaryl sulfones such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and bis (3-chloro-4-hydroxyphenyl) sulfone; bis (4-hydroxy Dihydroxydiaryl ethers such as phenyl) ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether; 4,4′-dihydroxybenzophenone, 3,3
Dihydroxydiaryl ketones such as', 5,5'-tetramethyl-4,4'-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide,
Dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide;
Dihydroxydiarylsulfoxides such as bis (4-hydroxyphenyl) sulfoxide; dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl;
And dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to the dihydric phenol compounds, dihydric phenol compounds such as dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; and dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene are exemplified.

In addition, phenolic compounds having a valency of 3 or more also include
The obtained PC-based resin can be used in a range that maintains thermoplasticity. Examples of the trivalent or higher phenolic compound include 2,4,4'-trihydroxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4,4'-trihydroxyphenyl ether,
2,2 ', 4,4'-tetrahydroxyphenyl ether, 2,4,4'-trihydroxydiphenyl-2-propane, 2,2'-bis (2,4-dihydroxy) propane, 2,2', 4,4′-tetrahydroxydiphenylmethane, 2,4,4′-trihydroxydiphenylmethane, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -3- [α ′, α′-bis ( 4 "-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -4
-[Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6- Bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 4,6-dimethyl-
2,4,6-tris (4'-hydroxyphenyl) -2
-Heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptane, 1,
3,5-tris (4'-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis [4,4-bis (4'-hydroxyphenyl) cyclohexyl] propane , 2,6-bis (2'-hydroxy-5'-isopropylbenzyl)-
4-isopropylphenol, bis [2-hydroxy-
3- (2'-hydroxy-5'-methylbenzyl) -5
-Methylphenyl] methane, bis [2-hydroxy-3
-(2'-hydroxy-5'-isopropylbenzyl)
-5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2 ', 4', 7-trihydroxyflavan, 2,4,4-trimethyl-2 ', 4 ', 7
-Trihydroxyflavan, 1,3-bis (2 ', 4'
-Dihydroxyphenylisopropyl) benzene, tris (4'-hydroxyphenyl) -amyl-s-triazine and the like.

These dihydric or higher phenol compounds may be used alone or in combination of two or more.

If necessary, the PC resin may contain, in addition to the phenolic compound having a valency of 3 or more, a component for forming a branched polycarbonate resin without impairing the chemical resistance, heat stability and mechanical properties. It can be contained in a range. Components (branching agents) other than the trivalent or higher phenolic compound used to obtain the branched polycarbonate resin include, for example, phloroglucin, melitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, and gallic acid. n-propyl, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-resorcinic acid, β-
Resorcinic acid, resorcinaldehyde, trimethyl chloride, isatin bis (o-cresol), trimethyl trichloride, 4-chloroformyl phthalic anhydride, benzophenone tetracarboxylic acid and the like.

As the PC resin, a polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate portion and a polyorganosiloxane portion may be used. The degree of polymerization of the polyorganosiloxane moiety is preferably 5 or more.

In addition, as the PC resin, for example, a copolymer containing a linear aliphatic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or decanedicarboxylic acid as a copolymer monomer. It can also be used.

As the components of the PC-based resin, if necessary, various known compounds used as a terminal stopper at the time of polymerization may be used in a range that does not impair the chemical resistance, heat stability and mechanical properties. Can be used with Specifically, monohydric phenol compounds such as phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, bromophenol,
Tribromophenol, nonylphenol and the like.

Examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate;
Examples thereof include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The viscosity-average molecular weight of the PC resin is not particularly limited, but is preferably 10,000 or more from the viewpoint of the strength and heat resistance of a molded article from the obtained composition.
Furthermore, it is 15,000 or more, especially 18,000 or more. Further, from the viewpoint of moldability, it is preferably at most 60,000, more preferably at most 45,000, particularly preferably at most 35,000.
000 or less.

Specific examples of the PC resin as described above include, for example, a polycarbonate resin obtained by reacting bisphenol A with phosgene or diphenyl carbonate, and a resin obtained by reacting bis (4-hydroxyphenyl) methane with diphenyl carbonate. Polycarbonate resin and the like. Further, in order to enhance the flame retardancy, a copolymer with a phosphorus compound (for example, a phosphorus compound having two or more OH groups in a molecule) (for example, a phosphorus compound having bisphenol A and two or more OH groups in a molecule) And a polymer end-blocked with a phosphorus-based compound (for example, a phosphorus compound having one OH group in a molecule). Further, a copolymer with a dihydric phenol having a benzotriazole group can be used to enhance the weather resistance.

The PC resins may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation on the combination, and for example, those having different monomer units, those having different copolymerization molar ratios, and those having different molecular weights can be arbitrarily combined.

Further, it may be used by mixing with another thermoplastic resin. Examples of other preferable thermoplastic resins which can be used by mixing with a PC resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate. Thermoplastics containing oxygen atoms in the molecular chain, such as resins, PPE resins, polyamide resins, poly (meth) acrylate resins, thermoplastic elastomers such as polyesters and polyamides, polystyrene, rubber-modified polystyrene, acrylonitrile Thermoplastic resins not containing an oxygen atom in the molecular chain, such as polystyrene resins such as styrene resin and acrylonitrile-butadiene-styrene resin, polyolefin resins, and thermoplastic elastomers such as olefin and styrene. Particularly preferred are a polyester resin in terms of balance between moldability and heat resistance, a poly (meth) acrylate resin in terms of balance between transparency and weather resistance, and a polystyrene resin in terms of moldability. .

The mixing ratio of the PC resin to the other thermoplastic resin is not particularly limited, and is arbitrarily selected according to the required characteristics. When the thermoplastic resin to be mixed contains no oxygen atom in the molecular chain, the proportion of the PC resin in the thermoplastic resin (A) is preferably 20% or more from the viewpoint of flame retardancy. In addition, when imparting other properties by suppressing the decrease in heat resistance and impact resistance of the PC resin, the proportion of the PC resin in the thermoplastic resin (A) is preferably 50% or more. .

The polyester resin preferably used as the thermoplastic resin (A) uses a divalent or higher carboxylic acid component or an ester-forming derivative thereof as an acid component.
A thermoplastic resin obtained by polycondensation by a known method using a dihydric or higher alcohol and / or a phenol component or an ester-forming derivative thereof as an alcohol component, and having heat resistance, chemical resistance, and mechanical properties. It is a resin used in fields where properties such as strength and moldability are required.

The divalent or higher valent aromatic carboxylic acid component or an ester-forming derivative thereof has 8 to 22 carbon atoms.
Or a divalent or higher aromatic carboxylic acid and an ester-forming derivative thereof. Specific examples of these include:
Phthalic acids such as terephthalic acid and isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-
Divalent aromatic carboxylic acids such as 4,4'-dicarboxylic acid and diphenylsulfone dicarboxylic acid, and trivalent or higher aromatic carboxylic acids such as trimesic acid, trimellitic acid, and pyromellitic acid, and ester-forming derivatives thereof. can give. Of these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferred in terms of easy handling, easy reaction, good moldability of the obtained resin, and the like. These may be used alone or in combination of two or more.

The dihydric or higher alcohol and / or phenol component or an ester-forming derivative thereof includes an aliphatic compound having 2 to 15 carbon atoms, an alicyclic compound having 6 to 20 carbon atoms, Examples include 6 to 40 aromatic compounds having two or more hydroxyl groups in a molecule, and ester-forming derivatives thereof. Specific examples thereof include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, and neopentyl glycol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol;
-Bis (4-hydroxyphenyl) propane, 2,2 '
Aromatic diols such as -bis (4-hydroxycyclohexyl) propane and hydroquinone; tri- or higher-valent alcohols such as glycerin and pentaerythritol; phenols; and ester-forming derivatives thereof. Among them, ethylene glycol, butanediol, and cyclohexane dimethanol are preferred in terms of easy handling, easy reaction, good moldability of the obtained resin, and the like.

The polyester-based resin may contain, in addition to the acid component and the alcohol and / or phenol component or their ester-forming derivatives, known copolymerizable components as long as desired properties are not impaired. It may be copolymerized.

Examples of such copolymerizable components include divalent or higher valent aliphatic carboxylic acids having 4 to 12 carbon atoms and 8 carbon atoms.
And carboxylic acids such as divalent or higher alicyclic carboxylic acids having up to 15 and ester-forming derivatives thereof.
Specific examples of these include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid,
Examples thereof include dicarboxylic acids such as 3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof. In addition, oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid and ester-forming derivatives thereof, and cyclic esters such as ε-caprolactone can also be used as the copolymerization component. Furthermore, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymerized polyethylene oxide addition polymer, propylene oxide addition polymer, tetrahydrofuran addition polymer, poly A polymer obtained by partially copolymerizing a polyalkylene glycol unit such as tetramethylene glycol in a polymer chain can also be used.

The proportion of the copolymerizable component to be copolymerized within a range that does not impair the properties of the polyester resin is as follows:
20% or less in polyester resin, and 15% or less
% Or less, particularly preferably 10% or less.

When the polyester-based resin contains 80% or more, more preferably 85% or more, especially 90% or more of the alkylene terephthalate repeating unit, the preferable characteristics of the polyalkylene terephthalate resin are maintained. The resulting composition is excellent in balance (for example, balance between moldability and mechanical strength).

The polyester resin has a logarithmic viscosity (IV) at 25 ° C. of 0.30 to 2.00 in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent.
dl / g, preferably 0.40 to 1.80 dl / g, particularly preferably 0.50 to 1.60 dl / g.
When the logarithmic viscosity (IV) is less than 0.30 dl / g, there are many cases where the flame retardancy and mechanical strength of the molded product become insufficient, and when it exceeds 2.00 dl / g, the molding fluidity decreases. Tend to.

Specific examples of the polyester resin include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

The polyester resins may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no limitation on how to combine them. For example, copolymer components, components having different molar ratios, and components having different molecular weights can be arbitrarily combined.

Further, the other thermoplastic resin which may be used by mixing with another thermoplastic resin and which can be used by being mixed with a polyester resin is, for example, P
Thermoplastic elastomers such as C-based resins, PPE-based resins, polyamide-based resins, polyester-based, polyamide-based thermoplastic elastomers, poly (meth) acrylate-based resins, etc. containing oxygen atoms in the molecular chain, polystyrene-based resins, polyolefins Thermoplastic resins containing no oxygen atom in the molecular chain, such as thermoplastic resins such as olefin-based resins and styrene-based thermoplastic elastomers. Of these, PC
A system resin is particularly preferred from the viewpoint of heat resistance.

The mixing ratio between the polyester resin and the other thermoplastic resin is not particularly limited, and is arbitrarily selected according to the required characteristics. When the thermoplastic resin to be mixed contains no oxygen atom in the molecular chain, the proportion of the polyester resin in the thermoplastic resin (A) is preferably 20% or more from the viewpoint of flame retardancy. In addition, when other properties are imparted while suppressing a decrease in the chemical resistance and moldability of the polyester resin, the proportion of the polyester resin in the thermoplastic resin (A) is preferably 50% or more. .

The PPE resin preferably used as the thermoplastic resin (A) has the general formula (I):

[0040]

Embedded image

(In the formula, ^one of R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is a bond, and the others are each selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a substituted hydrocarbon group. Which may be the same or different from each other), and is a resin used in fields requiring heat resistance, mechanical strength, and the like.

Specific examples of the hydrocarbon groups represented by R ^{1 to} R ⁵ in the general formula (I) and the substituted hydrocarbon groups include those having 1 to 1 carbon atoms.
10 alkyl groups (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc.) and a carbon number of 6 to
20 aryl groups (for example, a phenyl group having a phenyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like, a naphthyl group and the like), a carbon number of 6 to 20;
A hydrocarbon group such as an alicyclic alkyl group (for example, a cyclohexyl group having a cyclohexyl group, a methyl group, an ethyl group, etc., a decahydronaphthyl group); and a substituted hydrocarbon group obtained by substituting the hydrocarbon group with a hydroxyl group or the like. Is raised. Among these, a methyl group and an ethyl group are preferred from the viewpoint of balance between moldability and heat resistance.

The unit represented by the general formula (I) is preferably a 1,4-phenylene ether-based unit.
Specific examples thereof include a 1,4-phenylene ether unit, a 2-methyl-1,4-phenylene ether unit,
-Ethyl-1,4-phenylene ether unit, 2-propyl-1,4-phenylene ether unit, 2-butyl-
1,4-phenylene ether unit, 2,6-dimethyl-
1,4-phenylene ether unit, 2-methyl-6-ethyl-1,4-phenylene ether unit, 2,6-diethyl-1,4-phenylene ether unit, 2-ethyl-
6-propyl-1,4-phenylene ether unit, 2,
6-dipropyl-1,4-phenylene ether unit, 2
-Methyl-6-butyl-1,4-phenylene ether unit, 2-ethyl-6-butyl-1,4-phenylene ether unit, 2-ethyl-6-isopropyl-1,4-phenylene ether unit, 2-methyl -6-hydroxyethyl-1,4-phenylene ether unit, 2,3,6-
And a trimethyl-1,4-phenylene ether unit. These units may form a PPE-based resin alone, or may be formed by combining two or more kinds.

The reduced viscosity of the PPE resin (0.5 g /
dl in chloroform solution, measured at 30 ° C).
It is preferably at least 20 dl / g, more preferably at least 0.3 dl / g, from the viewpoint of mechanical strength and flame retardancy.
/ G or less, more preferably 0.8 dl / g or less from the viewpoint of moldability.

Preferred PPE resins include poly (2,6-dimethyl-1,4-phenylene ether),
Copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and o-cresol, 2,6-dimethylphenol, 2,3,6- And copolymers with trimethylphenol and o-cresol. These may be used alone or in combination of two or more. 2
When used in combination of more than one kind, there is no limitation on the combination, and for example, those having different copolymer components and molar ratios, those having different molecular weights, and the like can be used in any combination.

Further, other thermoplastic resins which may be used by being mixed with other thermoplastic resins and which can be used by being mixed with the above-mentioned PPE-based resin include, for example, PC
Thermoplastics containing oxygen atoms in the molecular chain of polyester-based resins, polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide-based resins, poly (meth) acrylate-based resins, thermoplastic elastomers such as polyester-based and polyamide-based Does not contain oxygen atoms in the molecular chains of resins, polystyrene, rubber-modified polystyrene, acrylonitrile-styrene resin, polystyrene resins such as acrylonitrile-butadiene-styrene resin, polyolefin resins, olefins, and thermoplastic elastomers such as styrene. Thermoplastic resins and the like. Particularly preferred are a polystyrene resin in terms of moldability, a polyamide resin in terms of heat resistance, and a polyester resin in terms of balance between moldability and heat resistance.

The mixing ratio between the PPE resin and the other thermoplastic resin is not particularly limited, and is arbitrarily selected according to the required characteristics. When the thermoplastic resin to be mixed contains no oxygen atom in the molecular chain, the proportion of the PPE resin in the thermoplastic resin (A) is preferably 20% or more from the viewpoint of flame retardancy. In addition, when the heat resistance and water resistance of the PPE resin are prevented from deteriorating and other properties are added,
The proportion of the PPE resin in the thermoplastic resin (A) is 50
% Is preferable.

The polyamide resin preferably used as the thermoplastic resin (A) is a thermoplastic resin having an amide bond formed from an amino acid, a lactam or a diamine and a dicarboxylic acid, and has heat resistance, chemical resistance, and water resistance. It is a resin used in fields where mechanical strength, moldability and the like are required.

Examples of the amino acids include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid; examples of lactams include ε-caprolactam and ω-laurolactam; Methylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4-dimethyl Octamethylenediamine, meta-xylylenediamine, para-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,8-bis (amino Methyl) Licyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl)
Examples of dicarboxylic acids such as piperazine and aminoethylpiperazine include adipic acid, suberic acid, azelaic acid,
Sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like can be mentioned.

The relative viscosity of the polyamide resin (phenol / 1,1,2,2-tetrachloroethane = 60/4)
0 (weight ratio), measured at 25 ° C. and 1 g / dl) is 1.5
-5.0 dl / g is preferred. At less than 1.5 dl / g, mechanical strength and flame retardancy are reduced, and 5.0 dl / g.
If it exceeds g, the moldability tends to decrease.

Specific examples of preferred polyamide resins formed from the above amino acids include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), and polyhexamethylene adipamide (nylon 66). Polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyundecaneamide (nylon 1)
1), polydodecaneamide (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TM
HT), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthal / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclohexyl) methanedodecamide (nylon PACM)
12), polybis (3-methyl-4-aminocyclohexyl) methandodecamide (nylon dimethyl PACM1)
2), polymethaxylylene adipamide (nylon MXD
6), polyundecamethylene terephthalamide (nylon 11T), and copolymerized amides thereof. Among these, nylon 46, nylon 6,
Nylon 66, Nylon 11, Nylon 12, Nylon MXD6, and the like are more preferable in terms of moldability, heat resistance, and water resistance. These polyamide resins may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation on the combination, and for example, copolymer components having different molar ratios and different molecular weights can be used in any combination.

Further, other thermoplastic resins which may be used by being mixed with another thermoplastic resin, and which can be used by being mixed with a polyamide resin, include, for example, P
Thermoplastic resins containing oxygen atoms, such as C-based resins, polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate, PPE-based resins, poly (meth) acrylate-based resins, polyester-based and polyamide-based thermoplastic elastomers, and polystyrene Thermoplastic resins that do not contain oxygen atoms, such as polystyrene resins such as rubber-modified polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, polyolefin resins, olefin resins, and styrene-based thermoplastic elastomers. . Particularly preferred are PPE resins in terms of balance between moldability and heat resistance, and polyester resins in terms of dimensional stability.

The mixing ratio between the PA resin and the other thermoplastic resin is not particularly limited, and is arbitrarily selected according to the required characteristics. When the thermoplastic resin to be mixed contains no oxygen atom in the molecular chain, the proportion of the PA resin in the thermoplastic resin (A) is preferably 20% or more from the viewpoint of flame retardancy. In addition, the heat resistance, water resistance,
In the case where a decrease in moldability or the like is suppressed and other properties are imparted, the ratio of the PA resin to the thermoplastic resin (A) is 5%.
It is preferably at least 0%.

The polystyrene resin used as the thermoplastic resin (A) is a vinyl aromatic polymer or a rubber-modified vinyl aromatic polymer. Examples of the vinyl aromatic polymer include styrene and o-methyl. Nucleic alkyl-substituted styrenes such as styrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, pt-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, etc. Homopolymers and copolymers of vinyl aromatic compounds such as α-alkyl-substituted styrene, copolymers of one or more vinyl aromatic compounds with one or more other vinyl compounds, and mixtures thereof Is raised.

Examples of the compound copolymerizable with the vinyl aromatic compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And maleimide compounds.

Examples of the rubber used for the rubber-modified vinyl aromatic polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, ethylene-propylene copolymer and the like. Can be Specific examples of the rubber-modified vinyl aromatic polymer include rubber-modified polystyrene (HIPS) and acrylonitrile-styrene-butadiene copolymer (AB
S resin).

The polyolefin-based resin used as the thermoplastic resin (A) is, in addition to polyolefin in a narrow sense, a thermoplastic and is a polydiene, a mixture of two or more of them, and furthermore, each of an olefin monomer and a diene monomer. It is a polyolefin-based resin as a broad concept including a copolymer composed of more than one kind. For example, ethylene,
Propylene, 1-butene, 1-pentene, isobutene,
Butadiene, isoprene, chloropyrene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, α , .Omega.-non-conjugated dienes and the like, and homopolymers or copolymers selected from one or a combination of two or more thereof, and a mixture of two or more homopolymers and copolymers thereof. Can be

Further, the polyolefin resin may be a resin obtained by copolymerizing another copolymerizable vinyl monomer. Examples of the vinyl monomer include an aromatic vinyl compound, an alkyl methacrylate, an alkyl acrylate, a glycidyl (meth) acrylate, a vinyl alkyl ether, an unsaturated nitrile compound, an unsaturated amino compound, and a dialkyl maleate. Esters, allyl alkyl ethers, diene compounds,
Other vinyl monomers are mentioned. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-
Specific examples of the methyl methacrylate include methyl styrene, vinyl toluene, divinyl benzene, and the like. Examples of the methyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, and t-butyl methacrylate. -Ethylhexyl,
Specific examples of alkyl acrylates such as stearyl methacrylate are methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Stearyl and the like, glycidyl (meth) acrylate as glycidyl acrylate, glycidyl methacrylate and glycidyl acrylate, and specific examples of vinyl alkyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl i-propyl ether, vinyl n-
Propyl ether, vinyl i-butyl ether, vinyl n-amyl ether, vinyl i-amyl ether, vinyl 2-ethylhexyl ether, vinyl octadecyl ether, and the like, specific examples of the unsaturated nitrile compound include acrylonitrile and methacrylonitrile. Specific examples of the unsaturated amino compound include acrylamide,
Examples of the dialkyl maleate include methacrylamide and the like. Examples of the dialkyl maleate include di-n-amyl maleate, di-i-butyl maleate, dimethyl maleate, di-n-propyl maleate, and di-maleic acid. -Octyl ester, maleic acid di-
Nonyl esters and the like are specific examples of allyl alkyl ethers, such as allyl ethyl ether and allyl n-octyl ether. Specific examples of the diene compound are dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, and cyclopentadiene. ,
Examples thereof include 1,5-norbonadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene, and 1,3-cyclooctadiene. Also, specific examples of other vinyl monomers include:
Examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, vinyl acetate, and N-phenylmaleimide. These may be used alone or in combination of two or more.

Preferred among the polyolefin resins are polyethylene resins, polypropylene resins, and olefin resins obtained by copolymerizing at least one alkyl (meth) acrylate.

Specific examples of the polyethylene resin include, in addition to ordinary polyethylene, high-density polyethylene,
Examples thereof include low-density polyethylene, linear low-density polyethylene, and a copolymer of ethylene and propylene. Also,
Specific examples of the polypropylene resin include syndiotactic polypropylene, isotactic polypropylene, and atactic polypropylene.

The olefin resin obtained by copolymerizing one or more alkyl (meth) acrylates is, specifically, a copolymer obtained from an olefin and an alkyl (meth) acrylate; And copolymers obtained from carbon monoxide and alkyl (meth) acrylate.

The copolymer comprising one or more olefins and an alkyl (meth) acrylate is generally one copolymer.
It can be obtained by radical polymerization of one or more olefins and one or more alkyl (meth) acrylates in the presence of a radical initiator, but the polymerization method is not limited to this, and is generally known. It can be polymerized using various known polymerization methods. The copolymer may take any copolymer form such as a random copolymer, a block copolymer, and a graft copolymer.

Specific examples of the olefin used for producing the copolymer include ethylene, propylene, 1-butene,
1-pentene and the like. These α-olefins may be used alone or in combination of two or more. Particularly preferred of the olefins is ethylene.

The alkyl group in the alkyl (meth) acrylate used in the production of the copolymer is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 8 or less carbon atoms, and more preferably 6 or less carbon atoms. Is particularly preferred. When the number of carbon atoms in the alkyl group exceeds 10, dispersion tends to occur in the resin composition.

Specific examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, and n -Propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate and the like. These may be used alone or in combination of two or more. Particularly preferred among the alkyl (meth) acrylates are methyl acrylate and ethyl acrylate.

The copolymerization ratio of the olefin to the alkyl (meth) acrylate in the copolymer is preferably 30/70 to 97/3 by weight (olefin / alkyl (meth) acrylate). Is 4
0/60 to 95/5, more preferably 50/50 to 9
0/10.

Specific examples of the olefin and the alkyl (meth) acrylate in the copolymer obtained from the olefin, carbon monoxide and the alkyl (meth) acrylate include the compounds described above.

Preferred olefins in the copolymer,
The amount of copolymerization with carbon monoxide and alkyl (meth) acrylate is 30 to 94%, preferably 40 to 90% for olefin, 1 to 40% for carbon monoxide, preferably 5 to 30%, The content of the alkyl (meth) acrylate is 5 to 69%, preferably 10 to 60%.

The melt index (MI) of the olefin resin used in the present invention (200 ° C., 2 kg load; JIS
(Based on K6730) is preferably 500 g / 10 min or less, and more preferably 300 g / 10 min or less. If the MI exceeds 500 g / 10 minutes, the thermal stability of the flame-retardant thermoplastic resin composition tends to decrease.

Examples of the thermoplastic elastomer used in the present invention include olefin-based, polyester-based, styrene-based, and polyamide-based thermoplastic elastomers. Specific examples thereof include ethylene-propylene copolymer, styrene-butadiene block copolymer, polyester ether copolymer, aromatic polyester aliphatic polyester copolymer, polyamide ether copolymer, polyamide ester copolymer, and aromatic polyester. Aliphatic polyamide aliphatic polyamide copolymers and the like.

As the red phosphorus (B) which is the component (B) used in the present invention, in addition to general red phosphorus, one kind such as a thermosetting resin coating, a metal hydroxide coating, a metal plating coating and the like can be used. Stabilized red phosphorus coated with the above coating is exemplified. When red phosphorus is used as stabilized red phosphorus, compared to using untreated red phosphorus, the generation of odor during molding processing is suppressed, and thin-wall moldability is improved. Preferred from the point.

The content of red phosphorus in the stabilized red phosphorus is 5
The content is preferably 0% or more from the viewpoint of flame retardancy, and more preferably 60% or more.

The thermosetting resin used for coating the stabilized red phosphorus is not particularly limited as long as it is a resin capable of coating red phosphorus, and specific examples thereof include a phenol-formalin-based resin and a urea-formalin-based resin. Resins, melamine-formalin resins, alkyd resins, and the like.
The metal hydroxide is not particularly limited as long as it is a compound capable of coating red phosphorus, and specific examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. The metal forming the metal plating film is not particularly limited as long as it is a metal that can coat red phosphorus by electroless plating, but Fe, Ni, Co,
Examples thereof include Cu, Zn, Mn, Ti, Zr, Al and alloys thereof. Further, these coatings may be coatings obtained by combining two or more of the above-mentioned materials, or coatings stacked in two or more layers.

Red phosphorus (B) has a particle size of red phosphorus having a particle size of 15 to 45 μm ≧ 50 number% (1) red phosphorus having a particle size of less than 15 μm ≦ 25 number% (2) a particle size of 45 μm Red phosphorus exceeding 25 number% (3) Red phosphorus having a particle size of 70 μm or less ≧ 90 number% (4) (the total is 100 number%). Incidentally, for example, the expression (1) indicates that
m indicates that the number of red phosphorus particles is 50% by number or more.

The particle size is a particle size when the red phosphorus particles are regarded as a sphere. For example, after a slurry of the red phosphorus particles is made into an appropriate solution, the particle size is measured using a particle counter or the like. It can be obtained together with the number by a method of measuring the distribution and determining the particle diameter and the number thereof, a method of obtaining a particle diameter and the number thereof by photographing the particles and performing image processing, and the like.

Further, as a method for obtaining red phosphorus (B) used in the present invention, for example, red phosphorus is dispersed in a dispersion medium such as water, and then separated into particles having a particle size of more than 70 μm and particles having a size of 70 μm or less. 45μm filter
The particles are passed through a filter capable of separating particles having a particle size of more than 45 μm or less and a filter capable of separating particles having a size of 15 μm or more and particles having a size of less than 15 μm, and classified to obtain red phosphorus compounds satisfying Formulas (1) to (4). Method, a method of mixing the classified red phosphorus in a desired ratio to obtain red phosphorus satisfying the formulas (1) to (4), and a pulverizing step in the production of red phosphorus to obtain a target particle diameter. Method to classify by mesh or air current, when converting yellow phosphorus to red phosphorus,
A method of obtaining the target red phosphorus by controlling the reaction temperature and the conversion rate, or a method of classifying with a mesh or an air stream after the conversion and the like can be mentioned.

When the particle size of the red phosphorus does not satisfy the formulas (1) to (4), for example, when the red phosphorus having a particle size of less than 15 μm exceeds 25% by number, it is mixed with an extruder or the like. When the dispersibility of red phosphorus is not sufficient, red phosphorus exceeding 45 μm exceeds 25% by number, mechanical strength such as tensile strength may decrease, and red phosphorus of 70 μm or less may be reduced to 90%. If it is less than a few percent, the mechanical strength such as the tensile strength is lowered and the variation in the flame retardancy is undesirably increased.

The red phosphorus compounds (B) may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation on the method of combination except that the formulas (1) to (4) are satisfied. For example, those having different coatings and those having different average particle diameters are arbitrarily combined. Can be used.

The content of the red phosphorus (B) is from 0.1 to 15 parts, preferably from 0.15 to 12 parts, more preferably from 0.2 to 15 parts, per 100 parts of the thermoplastic resin (A). 10
Department. If the content is less than 0.1 part, the flame retardancy of the obtained molded article is insufficient, and if it exceeds 15 parts, the tensile strength and the like are lowered depending on the type of the thermoplastic resin (A).

In the present invention, a fluorine resin and / or a silicone (C) as the component (C) can be used for the purpose of further improving the flame retardancy.

The fluororesin is a resin containing 10% or more, more preferably 20% or more, of fluorine atoms in the resin. Specific examples include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, and the like. If necessary, a monomer used for the production of the fluororesin within a range that does not impair the physical properties such as flame retardancy of the obtained molded article (usually a range where the content of fluorine atoms is 5% or more). A copolymer obtained by polymerization in combination with a monomer copolymerizable with (for example, α-olefin or the like) may be used. These fluororesins may be used alone.
A combination of more than one species may be used.

The fluororesin can be produced by a generally known method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and a solution polymerization method.

The above-mentioned silicones are (poly) organosiloxanes, such as monoorganosiloxanes such as dimethylsiloxane and phenylmethylsiloxane, polydimethylsiloxane and polyphenylmethylsiloxane obtained by polymerizing these. And organopolysiloxanes such as a copolymer of the above.

In the case of the above-mentioned organopolysiloxane, modified silicones having a molecular terminal substituted by an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group or a polyether group bonded by an ether bond are also useful. .

The form of the silicone is not particularly limited, and any form such as oil, gum, varnish, powder, and pellet can be used.

When the fluororesin and / or silicones (C) are added, the addition amount is 0.01 to 5 parts, preferably 0.03 to 4 parts, per 100 parts of the thermoplastic resin (A). And more preferably 0.05 to 3.5 parts. If the addition amount is less than 0.01 part, the effect of further improving the flame retardancy is small, and if it exceeds 5 parts, the moldability and the like are undesirably reduced.

The composition of the present invention further comprises a reinforcing filler (D) as a component (D) in order to improve heat resistance and the like.
Can be added.

Examples of the reinforcing filler (D) include fibrous reinforcing fillers (glass fibers, carbon fibers, potassium titanate fibers, etc.), glass beads, glass flakes, and silicate compound-based reinforcing fillers (having a chemical composition). A compound having a shape of powder, granule, needle, plate, etc. containing SiO ₂ units, such as magnesium silicate, aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin, Diatomaceous earth, smectite, etc., which may be a natural product or a synthetic one), calcium carbonate, calcium sulfate, barium sulfate, etc. Among them, silicate compound-based reinforcing fillers such as talc, mica, kaolin, smectite, especially mica and talc, and / or fibrous reinforcing fillers are preferred from the viewpoint of heat resistance.

The average particle size of the silicate compound-based reinforcing filler (the particle size when converted into a circle determined by image processing of a micrograph) is not particularly limited, but a preferable average particle size is 0. 0.01 to 100 μm, more preferably 0.1 to 50 μm, particularly preferably 0.3 to 100 μm.
４０40 μm. If the average particle size is less than 0.01 μm, the effect of improving the strength is not sufficient, and if it exceeds 100 μm, the toughness tends to decrease.

The silicate compound-based reinforcing filler may be treated with a surface treating agent such as a silane coupling agent or a titanate coupling agent. Examples of the silane coupling agent include epoxy silane, amino silane, vinyl silane, and the like.
Examples of titanate-based coupling agents include monoalkoxy type, chelate type and coordinate type.

The method of treating the silicate compound-based reinforcing filler with a surface treating agent is not particularly limited, and it can be treated by a usual method. For example, it can be carried out by adding a surface treatment agent to the layered silicate and stirring or mixing while heating. This treatment may be performed in a solution.

When the fibrous reinforcing filler is used, it is preferable to use chopped strand glass fibers treated with a sizing agent from the viewpoint of workability. Further, in order to enhance the adhesion between the resin and the fibrous reinforcing filler, it is preferable that the surface of the fibrous reinforcing filler is treated with a coupling agent,
A binder may be used. Examples of the coupling agent include the same as described above.

When glass fiber is used as the reinforcing filler (D), the diameter is 1 to 20 μm and the length is 0.01 to 50 mm
Are preferred. If the fiber length is too short, the effect of reinforcement is not sufficient, and if it is too long, the surface properties, extrudability, and moldability of the molded body are reduced.

The reinforcing filler (D) may be used alone.
It may be used in combination of more than one kind. When two or more kinds are used in combination, there is no particular limitation on the combination, but a preferable combination is a combination of two or more kinds of reinforcing fillers selected from mica, talc and glass fiber.

The addition amount of the reinforcing filler (D) is 0.5 to 100 parts, preferably 1 to 60 parts, and more preferably 2 to 40 parts based on 100 parts of the thermoplastic resin (A). If the addition amount is less than 0.5 part, the effect of improving heat resistance is small, and
If it exceeds 0 parts, the inherent properties of the thermoplastic resin tend to be impaired.

In order to make the composition of the present invention more sophisticated,
It is preferable to use an antioxidant such as a phenolic antioxidant and a thioether antioxidant, and a heat stabilizer such as a phosphorus stabilizer alone or in combination of two or more.
Further, if necessary, stabilizers such as light stabilizers which are generally well known, lubricants, release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant auxiliaries, ultraviolet absorbers, pigments, dyes, charging Additives such as an inhibitor, a conductivity-imparting agent, a dispersant, a compatibilizer, and an antibacterial agent can be used alone or in combination of two or more.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method in which the essential components of the present invention, other additives, resins and the like are dried and then melt-kneaded with a melt-kneading machine such as a single-screw extruder or a twin-screw extruder. Also, if the component is a liquid,
It can also be manufactured by adding to a melt kneader on the way using a liquid supply pump or the like.

The method of molding the composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resin compositions, such as injection molding, blow molding, extrusion molding, vacuum molding, It can be formed by a press molding method, a calendar molding method, a foam molding method, or the like.

The composition of the present invention is suitably used for various uses. Preferable applications include injection molded articles such as home appliances, OA equipment parts, and automobile parts, blow molded articles, extruded molded articles, foam molded articles, and the like.

[0100]

EXAMPLES Hereinafter, the composition of the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

The composition was evaluated by the following method.

(Preparation of sample) After drying the pellets,
Using an injection molding machine, 1/16 inch thick and 1/4 inch thick bars (12.7 mm wide, 127 mm long), AS
A TM1 dumbbell was manufactured and used.

(Flame retardancy and its variation) UL-94
According to the V standard, the flame retardancy of 20 1/16 inch bars was evaluated. At that time, the minimum value and the maximum value of the burning time (second) after the first flame contact were obtained, and the variation in flame retardancy was evaluated. The longer the burning time, the lower the flame retardancy, and the greater the difference between the minimum value and the maximum value, the greater the variation. In addition, when dripping occurs, the flame retardancy is low even if the burning time is short, and it becomes lower as the number of drippings increases.

(Tensile strength) Using a dumbbell, ASTM
A tensile test was performed according to D638, and the maximum strength (M
Pa) was determined.

(Dispersibility of Red Phosphorus) After drying the pellets,
Using a press machine, 280 ° C x 150 kg / cm ² G x 1
A 20 × 20 × 0.5 mm plate is manufactured by press-molding, and a light-transmitting sample is transmitted using an optical microscope.
The light-impermeable sample was observed by reflection, and the presence or absence of a place where the red phosphorus particles were clustered (aggregated) was evaluated. ：: Almost no aggregation sites △: There are aggregation sites and the number is 5 or less ×: There are aggregation sites and the number is 6 or more

(Heat resistance) Using a 1/4 inch bar, AS
According to TM D648, the deflection temperature under load (° C.) was measured at a load of 0.45 MPa, and the heat resistance was evaluated.

Example 1 100 parts of a bisphenol A-type polycarbonate resin (PC (A1)) having a viscosity average molecular weight of 23,000, 62% of red phosphorus having a particle size of 15 to 45 μm and coated with a phenol resin,
16% red phosphorus with a particle size of less than 15 μm, 22% red phosphorus with a particle size of more than 45 μm (93% of particles with a particle size of 70 μm or less)
2 parts of red phosphorus (red phosphorus content: 95%) (red phosphorus (B1)) composed of (number% measured by a fine particle counter using water as a dispersion medium), ADK STAB PEP-36 (Asahi Denka Kogyo Co., Ltd.) Product name) 0.5 parts, Adekastab AO-
After dry-blending 0.3 part of 60 (Asahi Denka Kogyo Co., Ltd., trade name), a twin-screw extruder equipped with a vent (TEX44: Nippon Steel Works Co., Ltd.) in which the cylinder temperature is set to 280 ° C.
The product was supplied to a hopper manufactured and manufactured by trade name and melt-extruded to obtain a resin composition, which was evaluated. Table 1 shows the results
Shown in

Examples 2 to 10 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the components shown in Table 1 were used in the amounts shown in Table 1. Table 1 shows the results
Shown in

Thermoplastic resin (A) PC (A2): bisphenol A type polycarbonate resin having a viscosity average molecular weight of 29000 PET (A3): polyethylene terephthalate having an logarithmic viscosity of 0.6 dl / g PET (A4): logarithmic viscosity of 0.8 dl / g of polyethylene terephthalate PBT (A5): polybutylene terephthalate of logarithmic viscosity 0.85 dl / g fluorinated resin and / or silicones (C) PTFE (C1): FA-500 (trade name, polytetra manufactured by Daikin Industries, Ltd.) Fluoroethylene) Silicone (C2): Si powder DC4-7051
(Product name, silicone manufactured by Toray Dow Corning Silicone Co., Ltd.)

Comparative Examples 1 to 6 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the components shown in Table 2 were used in the amounts shown in Table 2. Table 2 shows the results
Shown in

Red Phosphorus Red Phosphorus (b2): Particle size 1 coated with phenol resin
Red phosphorus consisting of 15% of red phosphorus of 5 to 45 μm, 85% of red phosphorus having a particle size of less than 15 μm, and 0% of red phosphorus having a particle size of more than 45 μm (100% of particles having a particle size of 70 μm or less) Red phosphorus (b3) : Particle size 1 coated with phenolic resin
Red phosphorus consisting of 35% of red phosphorus of 5 to 45 μm, 0% of red phosphorus having a particle diameter of less than 15 μm, and 65% of red phosphorus having a particle diameter of 45 μm (85% of particles having a particle diameter of 70 μm or less)

[0112]

[Table 1]

[0113]

[Table 2]

As is evident from the comparison between Table 1 as an example and Table 2 as a comparative example, by using red phosphorus having a specific particle size distribution, the dispersibility of the red phosphorus is good. It can be seen that the composition has excellent flame retardancy, small variations, and excellent tensile strength.

Examples 11 to 15 and Comparative Examples 7 to 9 Resin compositions were prepared in the same manner as in Example 1 except that the components shown in Table 3 were used in the amounts shown in Table 3 and the reinforcing filler (D) was added in the middle. I got something and evaluated it. Table 3 shows the results.

Reinforcement filler (D) Talc (D1): Microace K-1 (manufactured by Nippon Talc Co., Ltd., trade name, average particle size: about 3 μm) Mica (D2): A-21S (Yamaguchi Yamaguchi Co., Ltd.) Made, trade name, average particle size about 20 μm) Glass fiber (D3): T-195H / P (manufactured by NEC Corporation, trade name, average diameter about 10 to 15 μm, average length about 2 to 4 mm)

[0117]

[Table 3]

As is clear from the comparison between the examples and the comparative examples shown in Table 3, the dispersibility of the red phosphorus is good even in the reinforcing material by using the red phosphorus having a specific particle size distribution. It can be seen that the composition has excellent flame retardancy, small variation and excellent tensile strength.

Examples 16 to 22 and Comparative Examples 10 to 12 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the components shown in Table 4 were used in the amounts shown in Table 4. Table 4 shows the results
Shown in

Thermoplastic resin (A) PA-6 (A6): UBE nylon 1013B (trade name, nylon-6, manufactured by Ube Industries, Ltd.)
8 dl / g) PPE (A7): poly (2,6-dimethyl-) having a reduced viscosity of 0.5 dl / g measured at 30 ° C. in chloroform.
1,4-phenylene ether) resin PSt (A8): Estyrene HIH-65 (trade name, manufactured by Nippon Steel Chemical Co., Ltd., rubber-modified impact-resistant polystyrene) ABS (A9): Kaneace MUH (Kanebuchi Chemical Industry Co., Ltd.) (Trade name, acrylonitrile-butadiene-styrene resin) PE (A10): HIZEX 3000B (trade name, polyethylene, MI about 0.6, manufactured by Mitsui Petrochemical Industries, Ltd.)
g / 10 minutes) TPEE (A11): Hytrel 5557 (trade name, polyester thermoplastic elastomer manufactured by Du Pont-Toray Co., Ltd.)

[0121]

[Table 4]

As is clear from the comparison between the examples and the comparative examples shown in Table 4, the use of red phosphorus having a specific particle size distribution makes it possible to obtain good dispersibility of red phosphorus and flame retardancy. It can be seen that the dispersion is small, the dispersion is small, and the tensile strength is also excellent.

[0123]

According to the present invention, by using red phosphorus having a specific particle size distribution, the dispersibility of red phosphorus is good, the flame retardancy is excellent, the variation is small, and the tensile strength is low. Thus, an excellent flame-retardant resin composition can be obtained. These are very useful industrially.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 69/00 C08L 69/00 71/12 71/12 77/00 77/00 (72) Inventor Hiroshi Koyama Higashiizumi, Toyonaka-shi, Osaka Oka 3-3-20-302 (72) Inventor Kazufumi Hirobe 3-2-25-307 Honjo Nishi, Kita-ku, Osaka-shi

Claims (7)

[Claims] (B) Red phosphorus having a particle diameter of 15 to 45 μm ≧ 50% (1) Red phosphorus having a particle diameter of less than 15 μm ≦ 25% (2) Particles Red phosphorus exceeding 45 μm in diameter ≦ 25% (3) Red phosphorus having a particle diameter of 70 μm or less ≧ 90% (4) 0.1 to 15 parts by weight of a total of 100% (all in number%) of red phosphorus. And a flame-retardant thermoplastic resin composition. 2. The composition according to claim 1, wherein the thermoplastic resin (A) contains at least 20% by weight of a thermoplastic resin containing an oxygen atom in a molecular chain. 3. The composition according to claim 2, wherein the thermoplastic resin containing an oxygen atom in the molecular chain is at least one selected from a polycarbonate resin, a polyester resin, a polyamide resin, and a polyphenylene ether resin. Stuff. 4. A thermoplastic resin and / or silicone (C) based on 100 parts by weight of the thermoplastic resin (A).
4. The composition according to claim 1, wherein the composition is added in an amount of from 0.01 to 5 parts by weight. 5. The composition according to claim 1, further comprising (D) 0.5 to 100 parts by weight of a reinforcing filler per 100 parts by weight of the thermoplastic resin (A). 6. The composition according to claim 1, wherein the thermoplastic resin (A) is a polycarbonate resin and / or a polyester resin. 7. The red phosphorus (B) is selected from a thermosetting resin, a metal hydroxide, and a metal formed by plating.
A stabilized red phosphorus coated with at least one species.
The composition according to 2, 3, 4, 5 or 6.