JP2000256564A - Flame-retardant resin composition and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition causing no metal corrosion when subjected to dry heat treatment, excellent in mechanical properties and flowability, and useful for mechanical parts, electrical/electronic parts, etc., by incorporating a thermoplastic resin with red phosphorus, a phenolic resin and an amine-based compound in specified proportions. SOLUTION: This composition is obtained by incorporating (A) 100 pts. wt. of a thermoplastic resin such as polybutylene terephthalate resin, polyamide resin, polystyrene-based resin or polycarbonate resin with (B) 0.1-30 pts.wt. of red phosphorus (pref. 0.1-1,000 μS/cm in electroconductivity), (C) 0.1-15 pts.wt. of a phenolic resin such as of novolak type, and (D) 0.01-10 pts.wt. of an amine- based compound such as dicyandiamide or triazine-based compound, and furthermore (E) 5-140 pts.wt. of a filler such as glass fibers and/or (F) 0.01-10 pts.wt. of a fluororesin and/or silicone-based resin. Preferably, the other objective molded products including connectors, coil bobbins, relays, switches and housings are produced from the above composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition using a non-halogen flame retardant. More specifically, the present invention relates to a flame-retardant resin composition having excellent flame retardancy, mechanical properties, and fluidity, and particularly excellent in metal corrosion resistance after dry heat treatment, suitable for automobile parts, electric / electronic parts, and machine parts.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyester resins, polyamide resins, polystyrene resins, polycarbonate resins, and polyphenylene oxide resins make use of their excellent characteristics and are used as injection molding materials for mechanical and mechanical parts, electric and electronic parts, and automobiles. It is being used in a wide range of fields such as parts. On the other hand, since these thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary into the resin is generally used. However, this method tends to generate a large amount of smoke during combustion. Further, the resin composition containing the halogen-based flame retardant has a problem that the electric characteristics are deteriorated.

Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all.

Hitherto, as a method of making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, addition of red phosphorus has been disclosed in JP-A-5-78560 and JP-A-5-28771.
No. 19, JP-A-5-295164, JP-A-5-295164
-339417. However, although any resin composition is a useful flame-retardant resin material that does not use a halogen-based flame retardant, the effect of imparting high flame retardancy is insufficient, or the excellent mechanical properties of the thermoplastic resin are impaired. Had the problem that JP-A-10-251497 describes a method of blending red phosphorus and a novolak phenol resin with a polyester resin. However, a large amount of the novolak phenol resin is required to obtain sufficient flame retardancy. The mechanical properties were significantly reduced, and the resin composition of the present invention had the problem of causing metal corrosion by dry heat treatment.

[0006]

That is, the present invention uses a non-halogen flame retardant to impart a high degree of flame retardancy, and at the same time, has excellent mechanical properties and fluidity, as well as metal corrosion resistance after dry heat treatment. It is an object to obtain an excellent resin composition.

[0007]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies and as a result, have found that a thermoplastic resin containing red phosphorus,
By using amine compounds together with phenolic resins, it is possible to impart highly excellent flame retardancy, and at the same time, obtain resin materials that retain excellent mechanical properties and are particularly resistant to metal corrosion after dry heat treatment. And arrived at the present invention.

More specifically, the present invention relates to (1) (A) 100 parts by weight of a thermoplastic resin, (B) 0.1 to 30 parts by weight of red phosphorus,
(C) 0.1 to 15 parts by weight of a phenolic resin, and
(D) a flame-retardant resin composition comprising 0.01 to 10 parts by weight of an amine compound, (2) the flame-retardant resin composition according to (1), wherein the (D) amine compound is dicyanodiamide (3) The flame-retardant resin composition according to (1), wherein the (D) amine compound is a triazine compound, (4)
(B) The conductivity of red phosphorus is 0.1 to 1000 μS / cm (however, the conductivity is obtained by adding 100 mL of pure water to 5 g of red phosphorus, extracting at 121 ° C. for 100 hours, and filtering red phosphorus. Is the conductivity of the extraction water diluted to 250 mL.) (1) to (3), (5) the thermoplastic resin (A) 1
The flame-retardant resin composition according to any one of the above (1) to (4), further comprising 5 to 140 parts by weight of a filler with respect to 00 parts by weight, (6) 100 parts by weight of the thermoplastic resin (A) The above (1), which further contains 0.01 to 10 parts by weight of a fluorine-based resin and / or a silicone-based resin with respect to parts by weight.
(7) The flame-retardant resin composition according to any one of (1) to (5), wherein the thermoplastic resin (A) is a polyester resin.
To (6), (8) the flame-retardant resin composition according to (7), wherein the thermoplastic resin (A) is a polybutylene terephthalate resin, (9) thermoplasticity. (1) The flame-retardant resin composition according to any one of (1) to (6), wherein the resin (A) is a polyamide resin, and (10) the thermoplastic resin (A) is a polystyrene resin.
(11) The flame-retardant resin composition according to any one of the above (1) to (6), wherein the thermoplastic resin (A) is a polycarbonate resin.
(12) As the thermoplastic resin (A), a thermoplastic resin (a1) other than a polyethylene terephthalate resin and a polycarbonate resin, and a polyethylene terephthalate resin and / or
Alternatively, the combined use of the polycarbonate resin (a2) at a ratio of (a1) 50 to 99.9% by weight and (a2) 0.1 to 50% by weight with respect to the total of (a1) and (a2). The flame-retardant resin composition according to any one of the above (1) to (6), (13) a part of the thermoplastic resin (A) and red phosphorus (B) are once melt-kneaded to obtain a red phosphorus concentration. Is produced by melt-kneading the remaining thermoplastic resin (A) and the resin composition (E) having a high red phosphorus concentration by means of an extruder. (14) A method for producing a flame-retardant resin composition, which comprises producing the flame-retardant resin composition according to any one of (1) to (12). Molded article consisting of (1
5) The molded article according to the above (14), wherein the molded article is a mechanical mechanism part, an electric / electronic part, an OA equipment part, or an automobile part; and (16) the molded article is a connector, a coil bobbin, a relay, a switch, or a housing. ) Is provided.

[0009]

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

[0010] The thermoplastic resin (A) of the present invention is a synthetic resin which exhibits fluidity when heated, and can be molded by utilizing this.

Specific examples thereof include, for example, a vinyl (co) polymer rubber-modified styrene resin such as polystyrene and styrene / acrylonitrile copolymer (acrylonitrile / butadiene / styrene copolymer (ABS resin)).
(Styrene resin in the present invention refers to a resin in which an aromatic vinyl monomer is partially or wholly used as a raw material, and is a polymer blend of a styrene resin and polyphenylene oxide.) Modified polyphenylene oxide resin is included.), Polyester resin, liquid crystal polyester resin, polycarbonate resin, polyamide resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyoxymethylene resin, phenoxy resin, epoxy resin, polypropylene resin, polyethylene resin, ethylene / Propylene resin, ethylene / 1-butene resin, ethylene / propylene / non-conjugated diene resin, ethylene / ethyl acrylate resin, ethylene / glycidyl methacrylate resin, ethylene / vinyl acetate / g / meth acrylate Glycidyl resins, ethylene / vinyl acetate / glycidyl methacrylate resin, ethylene / propylene -g- anhydride olefin resin and maleic acid resin,
Examples include polyester polyether elastomers, elastomers such as polyester polyester elastomers, and mixtures of two or more of these thermoplastic resins.
Polystyrene, styrene / acrylonitrile copolymer,
Acrylonitrile / butadiene / styrene copolymer (A
BS resin), a polystyrene resin such as a modified polyphenylene oxide resin, a polyester resin, a polyamide resin, a polycarbonate resin, a phenoxy resin, a polyphenylene sulfide resin, or a mixture of two or more thereof. / Acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer (ABS resin), modified polyphenylene oxide resin and other polystyrene resins, polyester resins, polyamide resins, and polycarbonate resins. .

Among the above thermoplastic resins (A), the polyester resins substantially include polycondensates of dicarboxylic acids and glycols, ring-opening polymers of cyclic lactones, polycondensates of hydroxycarboxylic acids, and dibasic acids. And polycondensates of glycol and the like. Specifically, polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexane dimethylene terephthalate resin and polyethylene-1 , 2-bis (phenoxy) ethane-4,4'-dicarboxylate resin, and polyethylene-1,2
-Bis (phenoxy) ethane-4,4'-dicarboxylate resin, etc., and polyethylene isophthalate /
Copolymers and mixtures of terephthalate resin, polybutylene terephthalate / isophthalate resin, polybutylene terephthalate / decanedicarboxylate resin, and polycyclohexane dimethylene terephthalate / isophthalate resin can be exemplified. Particularly preferred polyester resins for the present invention include polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin, more preferably polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) resin. is there.

Although the molecular weight of such a polyester resin is not particularly limited, it is generally required that the intrinsic viscosity of the polyester resin measured at 25 ° C. using a 1: 1 mixed solvent of phenol / tetrachloroethane is from 0.1 to 3.0. But preferably 0.25 to 2.50, particularly preferably 0.40 to
2.25.

Among the thermoplastic resins (A), examples of the polyamide resin include a ring-opening polymer of a cyclic lactam, a polycondensate of an aminocarboxylic acid, and a polycondensate of a dibasic acid and a diamine. Specifically, nylon 6, nylon 66, nylon 46, nylon 610, nylon 61
2, aliphatic polyamides such as nylon 11, nylon 12, and poly (meta-xylene adipamide) (hereinafter referred to as MXD-6
Abbreviated), poly (hexamethylene terephthalamide)
(Hereinafter abbreviated as 6T), poly (nonamethylene terephthalamide) (hereinafter abbreviated as 9T), poly (hexamethylene isophthalamide) (hereinafter abbreviated as 6I), poly (tetramethylene isophthalamide) (hereinafter abbreviated as 4I) and the like. Examples thereof include aliphatic-aromatic polyamides, and copolymers and mixtures thereof. Particularly preferred polyamides for the present invention are nylon 6, nylon 66 and nylon 6/6.
6 copolymer, nylon 66 / 6T copolymer, nylon 6
T / 12 copolymer and nylon 6T / 6I / 12 copolymer can be mentioned.

Among the thermoplastic resins (A), polystyrene resins include vinyl (co) polymers such as polystyrene and styrene / acrylonitrile copolymer, rubber-modified styrene resins, rubber-modified styrene resins and polyphenylene. Polymer blends with an oxide (modified polyphenylene oxide resin) and the like can be mentioned.

Here, the rubber-modified styrenic resin refers to a graft polymer in which a rubbery polymer is dispersed in fine particles in a matrix made of an aromatic vinyl polymer. By adding an aromatic vinyl monomer and, if necessary, a vinyl mixture copolymerizable therewith to the monomer mixture by known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization. can get.

Examples of such rubber-modified styrene resins include impact-resistant polystyrene, ABS resin (acrylonitrile / butadiene / styrene copolymer), AA
S resin (acrylonitrile-acryl rubber-styrene copolymer), AES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer) and the like are exemplified.

As such a rubber-modified styrenic resin, one having a structure in which a (co) polymer containing an aromatic vinyl monomer is grafted to a rubbery polymer, one having an aromatic vinyl monomer (Co) polymer having a non-grafted structure to a rubbery polymer.

Specifically, 95 to 20 parts by weight of a monomer or monomer mixture containing 20% by weight or more of an aromatic vinyl monomer is graft-polymerized to 5 to 80 parts by weight of a rubbery polymer. The obtained (a) graft (co) polymer is obtained by polymerizing 5 to 100% by weight of a monomer or monomer mixture containing at least 20% by weight of an aromatic vinyl monomer and (b).
Those comprising from 0 to 95% by weight of a vinyl (co) polymer are preferred.

As the rubbery polymer, those having a glass transition temperature of 0 ° C. or less are suitable, and diene rubbers are preferably used. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer,
Examples include diene rubbers such as butyl acrylate-butadiene copolymer, acrylic rubbers such as polybutyl acrylate, polyisoprene, and ethylene-propylene-diene terpolymer. Among them, polybutadiene or butadiene copolymer is preferred.

Although the rubber particle diameter of the rubbery polymer is not particularly limited, the weight average particle diameter of the rubber particles is 0.15 to 0.6.
μm, especially 0.2 to 0.55 μm, is preferable because of its excellent impact resistance. Among them, 0.20 to 0.25 μm and 0.5
The weight ratio to 0 to 0.65 μm is 90:10 to 60:40.
Is preferable because the impact resistance and falling weight impact of a thin molded product are remarkably excellent.

The average weight particle size of the rubber particles is "Ru
bber Age Vol. 88p. 484-490
(1960) by E.I. Schmidt, P .; H. B
sodium salt alginate method described in “Idison” (particles having a cumulative weight fraction of 50% from the cumulative weight fraction of the creamed weight ratio and the sodium alginate concentration utilizing the fact that the particle size of polybutadiene to be creamed varies depending on the concentration of sodium alginate) (Determining the diameter).

Styrene as an aromatic vinyl monomer,
Examples include α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, etc., with styrene being particularly preferred.

As a monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer is used for the purpose of further improving impact resistance, and a (meth) acrylic monomer is used for the purpose of improving toughness and color tone. Acid ester monomers are preferably used. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable. Examples of the (meth) acrylate-based monomer include methyl and ethyl esters of acrylic acid and methacrylic acid with ethyl, propyl, n-butyl and i-butyl. Particularly, methyl methacrylate is preferred.

If necessary, other vinyl monomers,
For example, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide can be used.

The monomer or monomer mixture used in (a) the graft (co) polymer is preferably at least 20% by weight of an aromatic vinyl monomer from the viewpoint of the impact resistance of the resin composition. It is preferably at least 50% by weight. When a vinyl cyanide monomer is mixed, the amount is preferably 60% by weight or less, and more preferably 50% by weight or less, from the viewpoint of moldability of the resin composition. When a (meth) acrylate monomer is mixed, the content is preferably 80% by weight or less, more preferably 75% by weight or less from the viewpoint of toughness and impact resistance. The total amount of the aromatic vinyl-based monomer, vinyl cyanide-based monomer and (meth) acrylate-based monomer in the monomer or monomer mixture is preferably 95 to 20% by weight, and Preferably 90 to
30% by weight.

(A) The ratio of the rubbery polymer to the monomer mixture in obtaining the graft (co) polymer is preferably at least 5 parts by weight of the rubbery polymer based on 100 parts by weight of the total graft copolymer. More preferably, the amount is 10 parts by weight or more, and 80 parts by weight or less, more preferably 70 parts by weight or less. The amount of the monomer or monomer mixture is preferably 95 parts by weight or less, more preferably 90 parts by weight or less, and 2 parts by weight or less.
It is preferably at least 0 part by weight, more preferably at least 30 parts by weight, from the viewpoint of the impact resistance of the resin composition and the appearance of the molded product.

(A) The graft (co) polymer can be obtained by a known polymerization method. For example, it can be obtained by a method in which a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier are continuously supplied to a polymerization vessel in the presence of a rubbery polymer latex to carry out emulsion polymerization.

(A) The graft (co) polymer contains a non-grafted copolymer in addition to a material having a structure in which a monomer or a monomer mixture is grafted on a rubbery polymer. It is. (A) The graft ratio of the graft (co) polymer is not particularly limited, but is preferably from 20 to 80% by weight, particularly preferably from 25 to 50% by weight in order to obtain a resin composition having excellent impact resistance and gloss. .

Here, the graft ratio is calculated by the following equation. Graft ratio (%) = <amount of vinyl copolymer graft-polymerized on rubbery polymer> / <rubber content of graft copolymer> × 100

The properties of the non-grafted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component is 0.25 to 0.
6 dl / g, especially in the range of 0.25 to 0.5 dl / g,
N, N-dimethylformamide solvent, 0.25 to 0.75 dl / g, especially 0.35
Those having a range of from 0.7 to 0.7 dl / g are preferably used since a resin composition having excellent impact resistance can be obtained.

(B) The vinyl (co) polymer is a (co) polymer essentially containing an aromatic vinyl monomer. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, o-ethylstyrene, and the like.
Particularly, styrene is preferred. One or more of these can be used.

As a monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer is preferably used for the purpose of further improving impact resistance. For the purpose of improving toughness and color tone, (meth) acrylate monomers are preferably used. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable.
(Meth) acrylic ester monomers include acrylic acid and methacrylic acid methyl, ethyl, propyl, n
Examples thereof include an esterified product with -butyl and i-butyl, and methyl methacrylate is particularly preferable.

Further, as other vinyl monomers copolymerizable therewith, maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide can be used if necessary.

(B) From the viewpoint of the impact resistance of the resin composition, the proportion of the aromatic vinyl monomer as a component of the vinyl (co) polymer is preferably at least 20% by weight based on all monomers. Preferably, it is more preferably at least 50% by weight. When a vinyl cyanide monomer is mixed, the content is preferably 60% by weight or less, more preferably 50% by weight or less, from the viewpoint of impact resistance and fluidity. When a (meth) acrylate monomer is mixed, the amount is preferably 80% by weight or less, more preferably 75% by weight or less from the viewpoint of toughness and impact resistance. When other vinyl monomers copolymerizable therewith are mixed, the content is preferably 60% by weight or less, more preferably 50% by weight or less.

The properties of the vinyl (co) polymer are not limited, but the intrinsic viscosity [η] (methyl ethyl ketone solvent, 30 ° C.
Measurement) is 0.4 to 0.65 dl / g, especially 0.45 to
In the range of 0.55 dl / g, an N, N-dimethylformamide solvent, when measured at 30 ° C., 0.35 dl / g.
A resin composition in the range of from 0.85 dl / g to 0.45 dl / g, particularly from 0.45 to 0.7 dl / g, is preferred, since a resin composition having excellent impact resistance and moldability can be obtained.

The method for producing the vinyl (co) polymer is not particularly limited, and includes a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a bulk polymerization method.
Conventional methods such as a suspension polymerization method and a solution-bulk polymerization method can be used.

As the vinyl (co) polymer used in the present invention, a carboxyl group, a hydroxyl group,
A vinyl-based (co) polymer containing at least one functional group selected from an epoxy group, an amino group, and an oxazoline group (hereinafter, abbreviated as a modified vinyl-based (co) polymer) can also be used. The modified vinyl (co) polymer has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group, a hydroxyl group, an epoxy group, an amino group in the molecule. And a polymer containing at least one functional group selected from oxazoline groups. The content of the compound containing these functional groups is not limited, but is preferably in the range of 0.01 to 20% by weight in the modified vinyl (co) polymer.

The method for introducing a carboxyl group into the modified vinyl (co) polymer is not particularly limited, but includes acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, phthalic acid and itaconic acid. A method of copolymerizing a vinyl monomer having a carboxyl group or an anhydrous carboxyl group with a predetermined vinyl monomer,
γ, γ′-azobis (γ-cyanovaleic acid), α, α
Polymerization initiator having a carboxyl group such as' -azobis (α-cyanoethyl) -p-benzoic acid and succinic peroxide and / or thioglycolic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, α-mercapto- A method of (co) polymerizing a predetermined vinyl monomer using a polymerization degree regulator having a carboxyl group such as isobutyric acid and 2,3 or 4-mercaptobenzoic acid;
And copolymerization of (meth) acrylate monomers such as methyl methacrylate and methyl acrylate with aromatic vinyl monomers and, if necessary, vinyl cyanide monomers with alkali Can be used.

The method for introducing a hydroxyl group is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,2-acrylate acrylate 3,4,5,6-pentahydroxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-acrylic acid
Tetrahydroxypentyl, 2,3,4, methacrylic acid
5-tetrahydroxypentyl, 3-hydroxy-1-
Propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2
-Butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-
5-hydroxy-2-pentene, 4-dihydroxy-2
-A method of copolymerizing a vinyl monomer having a hydroxyl group such as butene with a predetermined vinyl monomer can be used.

The method for introducing an epoxy group is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p
-A method of copolymerizing a vinyl monomer having an epoxy group such as glycidyl ether or p-glycidyl styrene with a predetermined vinyl monomer can be used.

The method for introducing an amino group is not particularly limited. For example, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, methacryl Dimethylaminoethyl acrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-
A method of copolymerizing a vinyl monomer having an amino group such as aminostyrene or a derivative thereof with a predetermined vinyl monomer can be used.

The method of introducing an oxazoline group is not particularly limited. For example, vinyl having an oxazoline group such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2-styryl-oxazoline. For example, a method of copolymerizing a monomer with a predetermined vinyl monomer can be used.

The properties of the modified vinyl (co) polymer are not limited, but the intrinsic viscosity [η] (methyl ethyl ketone solvent, 3
0.degree. C.) is 0.2 to 0.65 dl / g, especially 0.3
In the range of 5 to 0.6 dl / g, and N, N-dimethylformamide solvent;
A resin composition having a flame retardancy, impact resistance, and moldability that is excellent is preferably from 0.9 to 0.9 dl / g, particularly from 0.4 to 0.75 dl / g.

The vinyl (co) polymer is preferably used as a rubber-modified styrenic resin in combination with the graft (co) polymer as described above, but may be used without being used in combination.

Among the above thermoplastic resins (A), the polycarbonate resin is obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. Usually, the viscosity average molecular weight is 10,000 to 10,000
00 range. Here, as the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl)
Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4 -Hydroxyphenyl)
Butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,
5-diethylphenyl) propane, 2,2-bis (4-
(Hydroxy-3,5-diethylphenyl) propane,
1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like can be used, and these can be used alone or as a mixture.

Further, by using a thermoplastic resin (a1) other than the polyethylene terephthalate resin and the polycarbonate resin as the thermoplastic resin (A) in combination with the polyethylene terephthalate resin and / or the polycarbonate resin (a2), a smaller amount of the resin can be obtained. A high degree of flame retardancy can be provided by the amount of the added flame retardant.

Among them, thermoplastic resins other than polyethylene terephthalate resin and polycarbonate resin (a1)
When a polybutylene terephthalate resin or a polyamide resin is used as the resin, the combined use of (a2) has a particularly large effect of improving the flame retardancy and can impart more excellent metal corrosion resistance, and thus can be preferably used.

The combination ratio of the above (a1) and (a2) ((a
(1) and (a2) are taken as 100% by weight) from the viewpoint of balance of flame retardancy, mechanical properties and fluidity.
0 to 99.9% by weight: (a2) preferably 0.1 to 50% by weight, more preferably (a1) 60 to 99% by weight:
(A2) 1 to 40% by weight, especially (a1) 70 to 90
% By weight: (a2) 10 to 30% by weight is preferred.

Next, the red phosphorus (B) used in the present invention will be described.

The red phosphorus (B) used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting with water gradually. What has been applied is preferably used. As a method for treating such red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and a red crushed surface having high reactivity with water and oxygen is not formed on the surface of red phosphorus. A method of finely dividing phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus,
A method of coating red phosphorus with paraffin or wax to suppress contact with moisture, a method of stabilizing by mixing with ε-caprolactam or trioxane, a method of mixing red phosphorus with phenolic, melamine, epoxy, or unsaturated polyester A method of stabilizing by coating with a thermosetting resin such as, red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to deposit a metal phosphorus compound on the red phosphorus surface Method of coating and stabilizing red phosphorus, method of coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., Electroless plating coating of red phosphorus surface with iron, cobalt, nickel, manganese, tin, etc. And a method in which these are combined.Preferably, without grinding the red phosphorus, A method of forming red phosphorus into fine particles without forming a crushed surface, a method of stabilizing red phosphorus by coating the same with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester type; Aluminum hydroxide, magnesium hydroxide, titanium hydroxide, a method of stabilizing by coating with zinc hydroxide,
Particularly preferred is a method of forming red phosphorus into fine particles without forming a crushed surface on the red phosphorus surface, by coating red phosphorus with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester type. A method of stabilizing the method, and a method of combining them. Among these thermosetting resins, red phosphorus coated with a phenolic thermosetting resin or an epoxy thermosetting resin can be preferably used from the viewpoint of moisture resistance, and particularly preferably a phenolic thermosetting resin. Red phosphorus coated with resin.

The average particle size of red phosphorus before being mixed with the resin is preferably from 50 to 0.01 μm, more preferably from the viewpoint of flame retardancy, mechanical strength and surface appearance of the molded product. , 45 to 0.1 μm.

The conductivity of the red phosphorus (B) used in the present invention when extracted in hot water (where the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, for example, in an autoclave at 121 ° C.). Extraction treatment at 100 ° C. for 100 hours, and measuring the conductivity of the extraction water obtained by diluting the filtrate after red phosphorus filtration to 250 mL) is the moisture resistance, mechanical strength, tracking resistance, and surface property of the obtained molded product. From 0.1 to 100
0 μS / cm, preferably 0.1 to 800 μS / cm.
cm, more preferably 0.1 to 500 μS / cm.

The amount of phosphine generated by the red phosphorus (B) used in the present invention (here, the amount of phosphine generated was determined by placing 5 g of red phosphorus in a 500-mL container (for example, a test tube) having a nitrogen content of 10 mmHg. After heat treatment at 280 ° C. for 10 minutes, cooling to 25 ° C., diluting the gas in the test tube with nitrogen gas to return to 760 mmHg, measuring using a phosphine (hydrogen phosphide) detector tube, The amount of phosphine generated (ppm) = indicated value of detector tube (ppm) × dilution factor) is the amount of gas generated in the composition, stability during extrusion and molding, mechanical strength during melt retention, From the viewpoint of the surface appearance of the molded article, corrosion of metal terminals by the molded article, etc., those having a concentration of usually 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less are used.
It is as follows.

Preferred commercial products of red phosphorus include “NOVA EXCEL” 140 and “NOVA EXCEL” F5 manufactured by Rin Kagaku Kogyo KK.

In the present invention, the amount of red phosphorus (B) added is
The amount is 0.1 to 30 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 27 parts by weight, and still more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the thermoplastic. If the amount is too small, the flame retardancy tends to be poor. On the other hand, if the amount is too large, the mechanical properties deteriorate, while the flame retardancy also deteriorates.

The phenolic resin (C) used in the present invention is not particularly limited as long as it is a polymer having a plurality of phenolic hydroxyl groups. For example, novolak-type, resol-type and heat-reactive resins, or modified resins thereof Resins. These may be an uncured resin, a semi-cured resin, or a cured resin without a curing agent added. Above all, a novolak type phenolic resin resin which is non-thermally reactive without the addition of a curing agent is preferred in terms of flame retardancy, mechanical properties and economic efficiency.

The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, and liquids can be used.

The phenolic resin (C) can be used alone or in combination of two or more, if necessary.

(C) The phenolic resin is not particularly limited, and commercially available phenolic resins and the like are used. For example, in the case of a novolak type phenol resin, phenols and aldehydes are charged into a reaction tank at a molar ratio of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid,
After adding a catalyst such as sulfuric acid or toluene sulfonic acid, the mixture is heated and subjected to a reflux reaction for a predetermined time, and then subjected to vacuum dehydration or standing dehydration to remove generated water, and further to the remaining water and unreacted phenols. Can be obtained. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components can be used alone or in combination of two or more.

In the case of a resol type phenol resin,
The molar ratio of phenols to aldehydes is 1: 1 to 1: 2
After charging into a reaction tank in such a ratio as follows, adding a catalyst such as sodium hydroxide, aqueous ammonia, and other basic substances, the same reaction and treatment as for the novolak-type phenol resin can be performed.

Here, phenols are phenol, o
-Cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-
Methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert
-Butyl-p-cresol and the like. One or more of these phenols can be used.
On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. One or more of these aldehydes can be used as needed.

The phenolic resin (D) used in the present invention may be 100 to 100 using a simultaneous thermogravimetric differential thermogravimeter (TG / DTA-200, manufactured by Seiko Instruments Inc.) in air. In a heating test performed in a temperature range of 600 ° C. at a heating rate of 40 ° C./min, the weight loss at 500 ° C. is preferably 50% or less, and in particular, it is preferable to use a material having a weight loss of 40% or less, It is preferable because high flame retardancy can be imparted and mechanical properties and heat resistance become better.

The molecular weight of the phenolic resin is not particularly limited, but is preferably 200 to 2,000 in number average molecular weight.
In particular, those having a range of 400 to 1,500 are preferable because of excellent mechanical properties, fluidity and economy. The phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a polystyrene standard sample.

In the present invention, the amount of the phenolic resin (C) is based on 100 parts by weight of the thermoplastic resin (A).
0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight,
More preferably, it is 0.5 to 7 parts by weight. When the blending amount of the (C) phenolic resin is within the above range, flame retardancy, fluidity, and surface appearance are improved.

In the present invention, the amine compound (D)
It has been found that, by adding together, a resin composition not only capable of imparting higher flame retardancy but also being free from metal corrosion even when subjected to dry heat treatment is obtained.

The amine compound (D) of the present invention includes
There is no particular limitation as long as it is a compound having one or more basic nitrogen atoms in the molecule, but those in which the amine compound has a boiling point equal to or higher than the melting and kneading temperature of the thermoplastic resin (A), It can be preferably used.

Specifically, such an amine compound (D)
Examples thereof include aliphatic amines such as tetramethylenediamine, hexamethylenediamine and dicyanodiamide, and aromatic amines such as diphenylamine, triphenylamine and triazine compounds, among which dicyanodiamide and triazine compounds are preferably used. it can.

The above-mentioned triazine compound is a compound having a triazine skeleton, for example, a compound represented by the following general formula (1).

[0070]

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In the general formula (1), R ¹ , R ² ,
R ³ and R ⁴ are the same or different, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -C
ONH ₂ . Here, the aryl group has 6 to 6 carbon atoms.
Preferred are those having 15 carbon atoms, those having 1 to 10 carbon atoms as alkyl groups, those having 7 to 16 carbon atoms as aralkyl groups, and those having 4 to 15 carbon atoms as cycloalkyl groups. The R is -NR ¹ R ² or -NR ³ R ⁴ the same group in the above formula, or their and independently hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH _2,
Or a group selected from -CONH _2, where the aryl groups those having from 6 to 15 carbon atoms, those having 1 to 10 carbon atoms as the alkyl group, the aralkyl group as 7 to 16 carbon atoms, The cycloalkyl group has 4 carbon atoms.
~ 15 are preferred.

Specific examples of R ¹ , R ² , R ³ and R ⁴ include hydrogen, phenyl, p-toluyl, α-naphthyl,
β-naphthyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group , A cycloheptyl group, a 2-methyl-1-pentyl group, a 4-methyl-1-cyclohexyl group, an amide group and the like, among which hydrogen, a phenyl group, a methyl group, a hydroxymethyl group, a methoxymethyl group, a benzyl group And an amide group is preferred.

Specific examples of R ⁵ include an amino group, an amide group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a mono (hydroxymethyl) amino group and a di (hydroxymethyl) amino group. , Mono (methoxymethyl) amino group, di (methoxymethyl)
Amino group, phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, among which hydrogen, an amino group, an amide group, a methyl group, a mono (hydroxymethyl) amino group, a di (hydroxymethyl) amino group, and a mono (methoxymethyl) group An amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferred.

Among them, melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,
3,5-Triazine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine and tri (hydroxymethyl) melamine are preferred, and melamine, benzoguanamine and acetoguanamine are particularly preferred. Furthermore, benzoguanamine and acetoguanamine are preferred from the viewpoint of sublimation during heating melt kneading or molding and mold corrosion inhibition, and benzoguanamine is particularly preferred.

The amount of the amine compound (D) is usually 0.01 to 100 parts by weight of the thermoplastic resin (A).
It is 10 parts by weight, preferably 0.1 to 7 parts by weight, more preferably 0.5 to 5 parts by weight.

The flame-retardant resin composition of the present invention can significantly improve strength, rigidity, heat resistance and the like by further adding a filler.

Such a filler may be fibrous or non-fibrous, such as granular. Specific examples thereof include:
Glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastenite,
Examples include glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.

The amounts of these additives are the same as those of the thermoplastic resin (A) 10
The amount is preferably from 5 to 140 parts by weight, particularly preferably from 5 to 100 parts by weight, per 0 parts by weight.

When the flame-retardant resin composition of the present invention is further added with a fluorine-based resin and / or a silicone-based compound, it is possible to suppress the drop (drip) of droplets during burning and to obtain a high-grade flame-retardant resin having a reduced burning time. Flame retardancy can be imparted.

Examples of the fluororesin include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer. Ethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene) / Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. , In particular polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

The silicone compound refers to a silicone resin and / or a silicone oil.

The silicone resin used in the present invention is
Chemically bonded siloxane units selected from units represented by the following general formulas (2) to (5) and mixtures thereof (where R is a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, Which represents a group selected from a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or allyl group), and has a number average molecular weight of 200 or more, and more preferably 1000 to 500.
Polymers in the range of 0000 are preferred in terms of flame retardancy, but are not limited to the above silicone resins.

[0083]

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The silicone oil used in the present invention is represented by the following general formula (6) (where,
R represents an alkyl group or a phenyl group, and n is an integer of 1 or more. ). The silicone oil used is 0.6
Those having a viscosity of 5 to 100,000 centistokes are preferred in terms of flame retardancy, but are not limited to the above silicone oils.

[0085]

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The addition amount of the fluororesin and / or silicone compound is usually 0.01 to 10 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the thermoplastic resin (A) from the viewpoint of mechanical properties and fluidity. 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

When the flame-retardant resin composition of the present invention uses a thermoplastic resin other than the olefin resin as the thermoplastic resin (A), the olefin resin is used as the thermoplastic resin (A). It has been found that when further added, the mechanical properties and the surface resistivity after wet heat treatment are improved without lowering the flame retardancy.

The olefin resin is used in an amount of 1 to 30 parts by weight, preferably 2 to 25 parts by weight, particularly preferably 3 to 30 parts by weight, per 100 parts by weight of the thermoplastic resin (A) other than the olefin resin.
It is preferable to add in the range of 20 parts by weight.

Examples of such olefin resins include polyethylene, ethylene copolymers and other olefin (co) polymers. Among them, polyolefin resins having a low glass transition temperature are preferably used.

The polyethylene may be any of high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene and the like.

The ethylene-based copolymer is a copolymer obtained by copolymerizing ethylene and a monomer copolymerizable therewith, among which ethylene is preferably copolymerized in an amount of 40 mol% or more. Examples of copolymerizable monomers include α-olefins such as propylene and butene-1, vinyl acetate, isoprene, butadiene, and monocarboxylic acids such as acrylic acid and methacrylic acid, and esters thereof, maleic acid, fumaric acid, and itaconic acid. And a dicarboxylic acid or an acid anhydride thereof. These may be copolymerized into the main chain, or those which can be graft-polymerized may be subjected to graft polymerization. These ethylene copolymers can be produced by a usual method.

Among them, preferred ethylene copolymers are copolymers obtained by grafting ethylene or ethylene and an α-olefin with an acid anhydride or glycidyl methacrylate or copolymerizing them with the main chain. Specifically, a copolymer obtained by copolymerizing ethylene and glycidyl methacrylate, or a copolymer obtained by graft-polymerizing an acid anhydride such as maleic anhydride to an ethylene-propylene copolymer is preferable.

As the copolymer obtained by copolymerizing ethylene and glycidyl methacrylate, a copolymer of a vinyl monomer such as styrene and a vinyl cyanide monomer such as acrylonitrile was graft-copolymerized. It may be something.

Examples of other olefin (co) polymers include copolymers obtained by grafting an acid anhydride or glycidyl methacrylate to an olefin compound or copolymerizing the glycidyl methacrylate into the main chain. Specifically, styrene and glycidyl are used. A copolymer obtained by copolymerizing methacrylate is preferred.

Among these ethylene copolymers and other olefin (co) polymers, copolymers obtained by grafting or copolymerizing an acid anhydride or glycidyl methacrylate are preferably used because of their good compatibility with the polyester resin.

These olefin resins can be used alone or in combination of two or more.

It has been found that, when the flame retardant resin composition of the present invention is further used in combination with a hindered phenol-based oxidation stabilizer, extremely good mechanical properties are maintained even when exposed to a high temperature for a long period of time. As such a stabilizer, for example, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

In the present invention, such a hindered phenol-based oxidation stabilizer can be added as needed, and the amount of the hindered phenol-based oxidation stabilizer added at that time is usually a thermoplastic resin ( A) 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.03 to 0.5 parts by weight, per 100 parts by weight.

The flame retardant resin composition of the present invention can further improve the stability, strength, heat resistance and the like during extrusion and molding by adding a metal oxide as a stabilizer for red phosphorus. Specific examples of such a metal oxide include:
Cadmium oxide, zinc oxide, cuprous oxide, cupric oxide,
Ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and titanium oxide, among which cadmium oxide, cuprous oxide,
Cupric oxide, titanium oxide is preferred, especially cuprous oxide,
Cupric oxide and titanium oxide are preferred.

The amount of the metal oxide added is preferably 0.0 to 100 parts by weight of the thermoplastic resin (A) in view of mechanical properties and moldability.
The amount is preferably 1 to 20 parts by weight, particularly preferably 0.1 to 1 part by weight.
0 parts by weight.

The flame-retardant resin composition of the present invention may further contain an epoxy group-containing compound for the purpose of improving the thermal stability and the hydrolysis resistance during melt processing.

Further, the flame-retardant resin composition of the present invention does not impair the object of the present invention, and does not impair the object of the present invention. One or more ordinary additives such as a lubricant, a releasing agent, and a coloring agent including a dye or a pigment can be added.

The flame-retardant resin composition of the present invention is produced by a generally known method. For example, thermoplastic resin (A), red phosphorus (B), phenolic resin (C), amine compound (D) and other necessary additives are premixed and supplied to an extruder or the like without or with premixing. It is prepared by sufficiently melting and kneading, but preferably, from the viewpoint of handling properties and productivity, a part or all of the thermoplastic resin (A) and red phosphorus (B) are once melt-kneaded and actually kneaded. A resin composition (E) having a higher red phosphorus concentration than the amount of red phosphorus to be blended in the flame-retardant resin composition is produced, and the remaining thermoplastic resin (A) has a higher red phosphorus concentration (E). ), Phenolic resin (C),
It is prepared by melt-kneading the amine compound (D) and other optional additives.

In the step of producing the resin composition (E) having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the flame-retardant resin composition as described above, it can be used arbitrarily. When the additives are blended, it is preferable that these optional additives are mixed with red phosphorus in advance.

Among the additives which can be used arbitrarily, when a metal oxide used as a stabilizer for red phosphorus, particularly titanium oxide, is added, the titanium oxide produces a red phosphorus-rich product (E). It is preferable to mix the red phosphorus and titanium oxide in advance using a mechanical mixing device such as a Henschel mixer to obtain the stability of the red phosphorus, the dispersibility of the red phosphorus, and the obtained resin composition. The non-coloring property of the product can be improved.

The content of red phosphorus in the high-concentration red-phosphorus product (E) is determined based on the production of the high-concentration red-phosphorus product, the dispersibility of red phosphorus, and the flame retardancy of the finally obtained resin composition. From the viewpoint of mechanical properties and moldability, the amount is preferably 30 to 300 parts by weight, particularly preferably 3 to 100 parts by weight of the thermoplastic resin (A).
5 to 200 parts by weight.

The resin composition (E) having a high red phosphorus concentration
Is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. The thermoplastic resin blended with the component (E) is preferably in the form of pellets, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture of a chip and a powder. Further, it is preferable that the form, size, and shape of the component (E) and the thermoplastic resin to be blended with the component (E) are substantially the same or similar to each other because they can be uniformly mixed. In producing the resin composition, for example, a single-screw extruder equipped with a “unimelt” type screw, a twin-screw extruder, a tri-screw extruder, and a kneader-type kneader can be used.

The resin composition (E) having a high red phosphorus concentration of the present invention imparts flame retardancy to a thermoplastic resin, and therefore can be used as a flame retardant for a thermoplastic resin.

The thermoplastic resin composition of the present invention is excellent not only in flame retardancy but also in mechanical properties, heat resistance and fluidity, and can be melt-molded, so that extrusion molding, injection molding, press molding and the like are possible. Yes, it can be formed into films, tubes, rods and molded products with any desired shape and size. Among them, it is particularly suitable for use in injection molded products.
It is also suitable for molded products with complicated shapes such as molded products having welds and hinges, insert molded products, and thin-walled molded products. It is also suitable for various mechanical mechanism parts, electrical and electronic parts, OA equipment parts, and automobile parts. is there.

For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, flyback transformers, focus cases, capacitors, variable condenser cases, optical pickups, oscillators, various terminals Plates, transformers,
Plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, computer related Electrical and electronic parts such as parts; VTR parts, TV parts, irons,
Home and office work represented by hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, washing jigs, oil-less bearings, stern bearings, underwater bearings, and other bearings, motor parts, lighters, typewriters, etc. Optical components such as microscopes, binoculars, cameras, clocks, etc., alternator terminals, alternator connectors, IC regulators, potentiometer bases for light deer, exhaust gas valves, etc. Seed valves, fuel related / exhaust / intake pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake Patware sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor Related parts, dust distributor, starter switch, starter relay, transmission wire harness, I command washer nozzles, air conditioner panel switch board, coil of magnetic valve for fuel supply, connectors for fuses, horn terminals, insulating plates for electric equipment, step motor rotor, lamp socket, lamp reflector, lamp housing,
It is useful for various applications such as brake pistons, solenoid bobbins, engine oil filters, and ignition device cases. Among the above, the features of the present invention, namely, flame retardancy,
It can be particularly suitably used for connectors, coil bobbins, relays, switches, and housings as parts that make use of mechanical properties, heat resistance, fluidity, and metal corrosion resistance.

[0111]

The effects of the present invention will be described in more detail with reference to the following examples.

Reference Example 1 (A) Thermoplastic resin <A-1> Toray PBT1100S (manufactured by Toray Industries, Inc.), which is a polybutylene terephthalate (PBT) resin, was used.

<A-2> The intrinsic viscosity is 0.65 (25 ° C.,
Phenol / tetrachloroethane 1: 1 mixed solvent)
Polyethylene terephthalate (PET) resin was used.

<A-3> Iupilon S3000 (manufactured by Mitsubishi Engineering-Plastics Corporation), which is a polycarbonate (PC) resin, was used.

<A-4> Amilan CM3001 (manufactured by Toray Industries, Inc.), which is a polyamide 66 (PA66) resin, was used.

<A-5> Preparation of Graft Copolymer The method for preparing the graft copolymer is described below. The graft ratio was determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. The solution was centrifuged at 8000 rpm (centrifugal force: 10,000 G
0 × 10 ³ m / s ² )) After centrifugation for 30 minutes, insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured.

Graft ratio = [(n)-(m) × L] /
[(M) × L] × 100 Here, L means the rubber content of the graft copolymer.

60 parts of polybutadiene latex (average rubber particle diameter 0.3 μm, gel content 85%) (in terms of solid content)
And 40 parts of a monomer mixture composed of 70% of styrene and 30% of acrylonitrile were added thereto to carry out emulsion polymerization. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer <A-5>.

The graft ratio of the obtained graft copolymer <A-5> was 36%. This graft copolymer <A
-5> represents a non-grafting copolymer composed of 70% of styrene structural units and 30% of acrylonitrile as 18.1.
%. The intrinsic viscosity of the N, N-dimethylformamide-soluble component was 0.48 dl / g.

<A-6> Preparation of Vinyl Copolymer A vinyl copolymer <A-6> was prepared by subjecting a monomer mixture composed of 70% of styrene and 30% of acrylonitrile to suspension polymerization. The obtained vinyl copolymer <A-6> is N,
The intrinsic viscosity of the N-dimethylformamide-soluble component is 0.73
Met.

Reference Example 2 (B) Red phosphorus <B-1>"NOVA EXCEL 140" (manufactured by Rin Kagaku Kogyo KK) was used.

Reference Example 3 (C) Phenolic resin <C-1>"Sumilite resin PR53195" which is a novolak type phenol resin (manufactured by Sumitomo Durez Co., Ltd.)
It was used.

Reference Example 4 (D) Amine Compound <D-1> Dicyanodiamide (reagent) was used.

<D-2> Benzoguanamine (reagent) was used.

Reference Example 5 (E) Thermoplastic Resin High Concentration of Red Phosphorus <E-1> 100 parts by weight of polybutylene terephthalate resin <A-1> shown in Reference Example 1 100 parts by weight of “NOVA EXCEL 140” manufactured by Kogyo Co., Ltd.) were mixed, and the screw diameter was 30 m while performing a nitrogen flow.
m, L / D = 45.5, using a coaxial rotary twin screw extruder (manufactured by Nippon Seiko Co., Ltd., TEX-30) to obtain a resin temperature of 260 to 2
It was melt-extruded at 80 ° C. to produce a polybutylene terephthalate red phosphorus-rich product <E-1>.

<E-2> Polyamide 6 shown in Reference Example 1
6 parts of resin <A-4> are mixed with 100 parts by weight of red phosphorus (“NOVA EXCEL 140” manufactured by Rin Kagaku Kogyo Co., Ltd.), and the screw diameter is 30 m while flowing nitrogen.
m, L / D = 45.5, using a coaxial rotary twin screw extruder (manufactured by Nippon Seiko Steel Co., Ltd., TEX-30) to obtain a resin temperature of 280-3.
Melt extrusion at 00 ° C, high concentration of red phosphorus of polyamide 66 <
E-2> was manufactured.

<E-3> 100 parts by weight of red phosphorus (“NOVA EXCEL 140” manufactured by Rin Kagaku Kogyo KK) was mixed with 100 parts by weight of the vinyl copolymer <A-6> shown in Reference Example 1. Then, while performing the nitrogen flow, screw diameter 30mm,
Using a coaxial rotary twin screw extruder (LEX / DEX = 45.5, manufactured by Nippon Seiko Co., Ltd., TEX-30), the resin temperature is 200 to 230.
Melt extrusion at ℃, high concentration of red phosphorus of vinyl copolymer <E
-3> was manufactured.

Reference Example 6 Other additives Glass fiber: "CS3PE941S" manufactured by Nitto Boseki Co., Ltd.
(Abbreviated as GF in the table) ・ Fluorine resin: “T6J” manufactured by Mitsubishi Fluorochemicals Co., Ltd. ・ Silicone compound: “DC4-7081” manufactured by Dow Corning Silicone Toray Co., Ltd.

Examples 1 to 14 and Comparative Examples 1 to 9 Red phosphorus (“NOVA EXCEL 140” manufactured by Rin Kagaku Kogyo Co., Ltd.) or the high concentration of red phosphorus shown in Reference Example 5 was added to 100 parts by weight of the thermoplastic resin. The product, phenolic resin, amine compound and other additives are mixed in the composition shown in Tables 1 to 4 and screw diameter is 30 m while performing nitrogen flow.
m, L / D 45.5 co-rotating twin-screw extruder (manufactured by Nippon Steel Co., Ltd., TEX-30: screw is a double-threaded screw and uses two screws of 3.5 mm, L / D = 4
Melting extrusion at a resin temperature of 220 to 290 ° C using a screw element consisting of 10 kneading disks inclined at 45 ° in the reverse order and a kneading force with a reverse full flight element. did. After the obtained pellets were dried, each test piece was molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS55EPN), and the physical properties were measured under the following conditions.

(1) Flame Retardancy Using the above-mentioned injection molding machine, test pieces for flame retardancy evaluation having the thicknesses shown in Tables 1 to 4 were molded, and the flame retardancy was evaluated in accordance with the evaluation criteria defined in UL94. The sex was evaluated. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB.

(2) Impact Resistance Impact resistance was evaluated according to ASTM D256-56A.

(3) Fluidity Injection speed: 99%, injection pressure: 500 kgf / cm at the cylinder temperature and mold temperature shown in the table using the above injection molding machine.
^Under the conditions of ² , the fluidity (flow length) was measured on a rod-shaped test piece having a thickness of 0.8 mm and a width of 12.7 mm.

(4) Metal Corrosion Resistance 100 g of resin composition pellets were put into a 500 ml wide-mouthed bottle capable of being sealed, a copper plate was placed thereon, and the mixture was sealed and subjected to a dry heat treatment at 150 ° C. for 50 hours in a gear oven. Thereafter, the surface of the copper plate was observed, and the metal corrosion resistance was evaluated by the following index. ○: Little change from the copper plate before dry heat treatment △: Part of the copper plate becomes black and corrosion is observed ×: The entire copper plate becomes black and extremely corroded Flame retardancy, impact resistance, The measurement results of fluidity and metal corrosion resistance are summarized in Tables 1 to 4.

When glass fibers were blended, they were blended so that the glass fiber weight% in the resin composition was 30%.

[0135]

[Table 1]

From the evaluation results of Examples 1 to 7 and Comparative Examples 1 to 4, the addition of PBT resin with red phosphorus, a phenolic resin and an amine compound specifically developed high flame retardancy, It is understood that a resin composition having excellent mechanical properties and fluidity and excellent metal corrosion resistance can be obtained.

On the other hand, sufficient flame retardancy cannot be obtained only by blending red phosphorus and a phenolic resin with the PBT resin (Comparative Example 1). It can be seen that the flame retardancy can be improved by increasing the amount of the phenolic resin, but the mechanical properties are greatly reduced, causing even worse metal corrosion (Comparative Example 2).

Further, PBT resin and P
When a mixture of ET resin or PC resin is used, P
It can be seen that, compared to the case of using only a BT resin, a resin composition which shows excellent flame retardancy by using a small amount of a flame retardant and does not corrode metal (copper plate) even after dry heat treatment can be obtained.

Further, it can be seen that when a high-concentration product of red phosphorus is used, it is possible to impart high flame retardancy with a further reduced burning time. Furthermore, by adding a fluorine-based resin or a silicone-based compound, it is possible to impart higher flame retardancy.

[0140]

[Table 2]

From the evaluation results of Examples 8 to 10 and Comparative Examples 5 to 7, it was found that by blending red phosphorus, a phenolic resin and an amine compound with the PA66 resin, high specific flame retardancy was exhibited, and It is understood that a resin composition having excellent mechanical properties and fluidity and excellent metal corrosion resistance can be obtained.

Further, when a PET resin or a PC resin is used in combination with the PA66 resin as the thermoplastic resin,
It can be seen that compared to the case of using only the resin alone, the use of a small amount of the flame retardant shows excellent flame retardancy and no metal corrosion.

[0143]

[Table 3]

[0144]

[Table 4]

Examples 11 to 12, Comparative Example 8, and Example 13
From the evaluation results of Comparative Examples 9 to 14, even when a PC resin or an ABS resin is used as the thermoplastic resin, a high degree of flame retardancy can be imparted by blending red phosphorus, a phenolic resin and an amine compound. In addition, it is understood that a resin composition having excellent mechanical properties and fluidity and excellent metal corrosion resistance can be obtained.

[0146]

(1) By mixing red phosphorus, a phenolic resin and an amine compound with a thermoplastic resin, the resin is excellent in flame retardancy, mechanical properties and fluidity and does not corrode metal even during dry heat treatment. A composition can be obtained. (2) The flame-retardant resin composition obtained by the present invention is not only excellent in flame retardancy but also an excellent flame-retardant formulation which does not adversely affect the properties of the thermoplastic resin. It has excellent corrosiveness and is useful as mechanical parts, electrical and electronic parts, and automobile parts.

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Claims (16)

[Claims] (A) 100 parts by weight of a thermoplastic resin, (B)
0.1 to 30 parts by weight of red phosphorus, (C) phenolic resin
1 to 15 parts by weight and (D) amine compound 0.01
A flame-retardant resin composition containing 10 to 10 parts by weight. 2. The flame-retardant resin composition according to claim 1, wherein the amine compound (D) is dicyanodiamide. 3. The flame-retardant resin composition according to claim 1, wherein the amine compound (D) is a triazine compound. 4. The red phosphorus (B) has a conductivity of 0.1 to 1000 μm.
S / cm (however, conductivity is 5 g of red phosphorus and 10 g of pure water).
After adding 0 mL and performing an extraction treatment at 121 ° C. for 100 hours, the liquid after filtration of red phosphorus is diluted to 250 mL to obtain the conductivity of the extracted water. The flame-retardant resin composition according to any one of claims 1 to 3, wherein 5. The composition according to claim 1, further comprising 5 to 140 parts by weight of a filler based on 100 parts by weight of the thermoplastic resin (A).
5. The flame-retardant resin composition according to any one of items 4 to 4. 6. A fluorine-based resin and / or a silicone-based resin in an amount of 0.01 part by weight per 100 parts by weight of the thermoplastic resin (A).
The flame-retardant resin composition according to any one of claims 1 to 5, further comprising 10 to 10 parts by weight. 7. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyester resin. 8. The flame-retardant resin composition according to claim 7, wherein the thermoplastic resin (A) is a polybutylene terephthalate resin. 9. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyamide resin. 10. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polystyrene resin. 11. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polycarbonate resin. 12. A thermoplastic resin (A) comprising a thermoplastic resin (a1) other than a polyethylene terephthalate resin and a polycarbonate resin, and a polyethylene terephthalate resin and / or a polycarbonate resin (a2);
(A1) 50-99.
The flame-retardant resin composition according to any one of claims 1 to 6, wherein 9% by weight and (a2) 0.1 to 50% by weight are used in combination. 13. A part of the thermoplastic resin (A) and red phosphorus (B) are once melt-kneaded to produce a resin composition (E) having a high red phosphorus concentration, and the remaining thermoplastic resin (A) and The flame-retardant resin composition according to claim 1, wherein the resin composition (E) having a high red phosphorus concentration is melt-kneaded with an extruder to produce the flame-retardant resin composition according to claim 1. Manufacturing method. 14. A molded article comprising the flame-retardant resin composition according to claim 1. 15. The molded article is a mechanical mechanism part, an electric / electronic part,
The molded article according to claim 14, which is an OA equipment part or an automobile part. 16. The molded article according to claim 14, wherein the molded article is a connector, a coil bobbin, a relay, a switch, or a housing.