JP2002121405A - Flame-retardant resin composition and molded article composed of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin having excellent flame retardance and light resistance without impairing mechanical characteristics of the thermoplastic resin. SOLUTION: This flame-retardant resin composition comprises (A) 100 pts.wt. thermoplastic resin, (B) 0.1 to 20 pts.wt. modified phenolic resin represented by general formula (1) [wherein R1 is a 1-10C organic residue; R2 is hydrogen atom or a 1-5C alkyl group] and (C) 1 to 30 pts.wt. phosphorus-based flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent flame retardancy and light resistance without impairing the mechanical properties (impact resistance and heat resistance) inherent in the thermoplastic resin.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have excellent mechanical properties, moldability, and electrical insulation properties, so that they can be used in household electric appliances and O.D.
It is used in a wide range of fields including various components such as A equipment and automobiles. However, depending on the use, flame retardancy is required due to safety issues, and various techniques have been proposed for flame retardancy.

[0003] Generally, a method is employed in which a halogen-based flame retardant such as a bromine compound having a high flame-retardant efficiency and antimony oxide are blended with a resin to make the resin flame-retardant. However,
This method has problems such as a large amount of smoke generated during combustion.

[0004] Therefore, in order to overcome these drawbacks of halogen-based flame retardants, a flame-retardant resin containing no halogen has been strongly desired in recent years.

As a non-halogen flame retardant, there is a phosphorus flame retardant, and a phosphoric ester has been often used as a typical one. For example, a method of adding a polyphosphate to a thermoplastic resin (JP-A-59-24736),
A method of adding a phosphate having a specific structure to rubber-reinforced styrene (Japanese Patent Application Laid-Open No. H11-140270) and a method of adding a liquid phosphate to a styrene-based resin (Japanese Patent Application Laid-Open No. H11-5869) have already been disclosed. I have.

However, thermoplastic resins, such as styrene resins, are generally extremely flammable, so that phosphate esters have extremely low flame-retardant effects, and are disclosed in JP-A-59-24736 and JP-A-59-24736. 11-14027
No. 0, JP-A No. 11-5869, the composition obtained by the method described in JP-A-11-5869, in order to impart flame retardancy to the thermoplastic resin, a large amount of phosphate ester must be blended, therefore, mechanical In addition to deteriorating the properties, there were problems such as bleeding out of the phosphate ester, mold contamination during molding, and generation of gas during molding.

As a method for solving the above problems, a method using a hydroxyl group-containing phosphoric acid ester is disclosed in Japanese Patent Application Laid-Open No. Hei 5
-247315.

However, the phosphoric acid ester containing a hydroxyl group also has an extremely low flame retarding effect, and it has been difficult to solve the above problems.

[0009] Phosphate esters have a low flame retardant effect,
In order to improve the flame retardancy, we have found that flame retardancy is improved by using melamine cyanurate as a flame retardant aid in addition to the phosphate ester. The problem that the properties, impact resistance and moldability were impaired could not be solved.

In order to further improve the flame retardancy, a method of adding a novolak phenol resin and a compound having a triazine skeleton as a carbonized layer-forming polymer to a hydroxyl group-containing phosphate ester is disclosed in JP-A-7-704.
No. 48 discloses this.

This technique cannot solve the problem that the mechanical properties, impact resistance and moldability inherent in thermoplastic resins are impaired. Further, since phenol resin is a material having extremely poor light resistance, there is also a problem that the light resistance of the obtained resin composition is reduced.

[0012]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a resin composition having excellent mechanical properties and heat resistance, and particularly excellent light resistance, while imparting high flame retardancy to a thermoplastic resin. The purpose is to provide.

[0013]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present invention provides excellent flame retardancy by blending a thermoplastic resin with a phosphorus-based flame retardant and a specific modified phenolic resin. It has been found that, in addition to being able to impart properties, light resistance is improved and mechanical properties, impact resistance and heat resistance are excellent.

That is, the present invention relates to (A) 100 to 100 parts by weight of a thermoplastic resin, (B) 0.1 to 20 parts by weight of a modified phenolic resin represented by the following general formula (1),
(C) A flame retardant resin composition containing 1 to 30 parts by weight of a phosphorus-based flame retardant. ".

[0015]

Embedded image (In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms.
R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )

[0016]

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

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 polystyrene resins such as polystyrene resins, styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene copolymers (ABS resins), polyester resins, polycarbonate resins, polyamide resins, and polyphenylene oxide. Resin, modified polyphenylene oxide resin, polyphenylene sulfide resin, polyoxymethylene resin,
Polyolefin resin such as polypropylene resin and polyethylene, ethylene / propylene resin, ethylene / 1-
Butene resin, ethylene / propylene / non-conjugated diene resin, ethylene / ethyl acrylate resin, ethylene / glycidyl methacrylate resin, ethylene / vinyl acetate / glycidyl methacrylate resin, ethylene / vinyl acetate / glycidyl methacrylate resin, ethylene / propylene -G
Elastomers such as maleic anhydride resins, polyester polyether elastomers, polyester polyester elastomers, and mixtures of two or more of these thermoplastic resins, such as polystyrene resins, styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene copolymers; One or a mixture of two or more selected from a polystyrene resin such as a polymer (ABS resin), a modified polyphenylene oxide resin, a polyester resin, a polyamide resin, a polycarbonate resin, and a polyphenylene sulfide resin is more preferable.
One or a mixture of two or more selected from polystyrene resins such as polystyrene resin, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer (ABS resin), polyester resin, polycarbonate resin, and polyamide resin.

Among the thermoplastic resins (A), polystyrene resins include polystyrene, styrene / acrylonitrile copolymer, rubber-modified styrene resin, and polymer blends of rubber-modified styrene resin and polyphenylene oxide ( Modified polyphenylene oxide resin).

The rubber-modified styrenic resin is obtained by adding a monomer mixture obtained by adding an aromatic vinyl monomer and optionally a vinyl monomer copolymerizable therewith in the presence of a rubber-like polymer. It can be obtained by subjecting to known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization.

Specific examples of such a rubber-modified styrene resin include, for example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acryl rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene propylene rubber). -Styrene copolymer).

As such a rubber-modified styrenic resin, one having a structure in which a (co) polymer containing a styrene monomer is grafted to a rubbery polymer and one containing a styrene 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 with 5 to 80 parts by weight of a rubbery polymer. (A1) graft (co) polymer 5 obtained by
100% by weight and 0 to 95% by weight of (a2) a vinyl (co) polymer obtained by polymerizing a monomer or a monomer mixture containing at least 20% by weight of an aromatic vinyl monomer. 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, the use of polybutadiene or butadiene copolymer is preferred.

The rubber particle diameter of the rubbery polymer is not particularly limited, but 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 excellent impact resistance. Among them, those having a weight average particle size of 0.20 to 0.25 μm and those having a weight average particle size of 0.50 to 0.65
Those having a weight ratio of 90:10 to 60:40 with respect to those of μm are preferred because of their excellent impact resistance and falling weight impact of thin molded products.

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

Specific examples of the aromatic vinyl monomer include:
Styrene, α-methylstyrene, vinyltoluene, o-
Ethyl styrene and pt-butyl styrene are exemplified, but the use of styrene is particularly preferred.

As the monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer is used for the purpose of further improving impact resistance, and a monomer for the purpose of improving toughness and color tone. In such a case, the (meth) acrylate monomer is
Each is preferably used.

Specific examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferably used.

Specific examples of the (meth) acrylic ester-based monomer include methyl, ethyl, propyl, n-butyl and i-butyl esters of acrylic acid and methacrylic acid. Particularly, methacrylic acid Methyl is preferably used.

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

From the viewpoint of the impact resistance of the resin composition, the monomer or monomer mixture used in the (a1) graft (co) polymer contains not less than 20% by weight of an aromatic vinyl monomer. Preferably, it is at least 50% by weight. When a vinyl cyanide monomer is mixed, from the viewpoint of moldability of the resin composition, 60% by weight is used.
Or less, particularly preferably 50% by weight or less. When a (meth) acrylate-based monomer is mixed, the content is preferably 80% by weight or less, particularly 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 95 to 20% by weight. Is preferred,
More preferably, it is 90 to 30% by weight.

(A1) The mixing ratio of the rubbery polymer and the monomer mixture in obtaining the graft (co) polymer is 100 parts by weight of the total graft copolymer from the viewpoint of the impact resistance of the resin composition. The content of the rubbery polymer is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. Also,
From the viewpoint of the impact resistance of the resin composition and the appearance of the molded product, the amount is preferably 80 parts by weight or less, more preferably 70 parts by weight or less. The mixing ratio of the monomer or the monomer mixture is 95 parts by weight or less, preferably 9 parts by weight.
0 parts by weight or less, or 20 parts by weight or more, preferably 3 parts by weight
0 parts by weight or more.

(A1) 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 in the presence of a rubbery polymer latex are continuously supplied to a polymerization vessel and emulsion polymerization is performed. .

(A1) The graft (co) polymer includes, in addition to a graft copolymer having a structure in which a monomer or a monomer mixture is grafted to a rubbery polymer, a non-grafted copolymer. It contained. The graft ratio of the graft (co) polymer is not particularly limited, but in order to obtain a resin composition having excellent impact resistance and gloss, it is preferable that the graft ratio be from 20 to 20.
It is preferably in the range of 80% by weight, especially 25 to 50% by weight. Here, the graft ratio is a value calculated by the following equation.

Graft ratio (%) = [<amount of vinyl copolymer graft-polymerized on rubbery polymer> / <rubber content of graft copolymer>) × 100 of ungrafted (co) polymer The properties are not particularly limited, but the intrinsic viscosity [η] of the methyl ethyl ketone soluble component
(Measured at 30 ° C.) is preferably in the range of 0.25 to 0.6 dl / g, particularly 0.25 to 0.5 dl / g, in order to obtain a resin composition having excellent impact resistance. It is.

(A2) The vinyl (co) polymer is a copolymer essentially containing an aromatic vinyl monomer. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, and o-ethylstyrene, and styrene is particularly preferably used. One or more of these can be used.

As a monomer other than the aromatic vinyl-based monomer, a vinyl cyanide-based monomer is preferably used in order to further improve the impact resistance. For the purpose of improving toughness and color tone, (meth) acrylate monomers are preferably used.

Specific examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferably used. Specific examples of (meth) acrylate monomers include methyl, ethyl, propyl, n-butyl, and i-acrylic acid and methacrylic acid.
Examples thereof include an esterified product with butyl, and particularly preferred is methyl methacrylate.

Other vinyl monomers which can be used as required and which can be copolymerized with these include maleimide,
Maleimide monomers such as N-methylmaleimide and N-phenylmaleimide are exemplified.

In the present invention, a vinyl copolymer obtained by copolymerizing a maleimide monomer, that is, a maleimide group-modified vinyl copolymer is used by being contained in a polystyrene resin. Can improve the heat resistance of
Furthermore, since flame retardancy can be specifically improved, it can be preferably used.

(A2) 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 at least 20% by weight based on all monomers. Is more preferable, and more preferably in the range of 50% by weight or more.
When a vinyl cyanide-based monomer is mixed, the content is preferably 60% by weight or less, and more preferably 50% by weight or less, from the viewpoint of impact resistance and fluidity. Also,
When a (meth) acrylate-based 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.
Further, when other vinyl monomers copolymerizable therewith are mixed, the content is preferably 60% by weight or less, particularly preferably 50% by weight or less.

(A2) The properties of the vinyl-based (co) polymer are not limited, but 30
The intrinsic viscosity [η] measured at 0.4 ° C. is 0.4 to 0.65 dl.
/ G, especially in the range of 0.45 to 0.55 dl / g, also using N, N-dimethylformamide solvent,
When measured at 30 ° C., 0.35 to 0.85 dl /
g, and particularly preferably in the range of 0.45 to 0.7 dl / g, since a resin composition having excellent impact resistance and moldability can be obtained.

(A2) The method for producing the vinyl (co) polymer is not particularly limited, and is usually a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk-suspension polymerization method or a solution-bulk polymerization method. Can be used.

In the present invention, a modified vinyl polymer containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group and an oxazoline group (hereinafter referred to as a modified vinyl Abbreviated as a polymer).

The modified vinyl polymer has a structure obtained by polymerizing or copolymerizing one or more vinyl monomers, and has a carboxyl group, hydroxyl group, epoxy group, It is a polymer containing at least one functional group selected from an amino group and an oxazoline group. Although the content of the compound containing these functional groups is not limited, in particular, the modified vinyl polymer 1
It is preferably in the range of 0.01 to 20% by weight per 100 parts by weight.

The method for introducing a carboxyl group into the modified vinyl polymer is not particularly limited. Examples of the method include 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 the hydroxyl group is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate , 3,4,5,6-pentahydroxyhexyl, methacrylic acid 2,3,4,5,6
Pentahydroxyhexyl, acrylic acid 2,3,4
5-tetrahydroxypentyl, methacrylic acid 2,3
4,5-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-
A method in which a vinyl monomer having a hydroxyl group such as 2-butene is copolymerized with a predetermined vinyl monomer can be used.

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

Among them, when the epoxy-modified vinyl copolymer having an epoxy group introduced by copolymerizing glycidyl methacrylate is used in a polystyrene resin, the flame retardancy of the resin composition of the present invention is reduced. , The impact strength can be improved.

The method for introducing the amino group is not particularly limited. For example, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, Dimethylaminoethyl methacrylate, 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 and a derivative thereof with a predetermined vinyl monomer can be used.

The method for introducing the 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 polymer are not limited, but the intrinsic viscosity [η] measured at 30 ° C. using a methyl ethyl ketone solvent is 0.2 to 0.65 dl / g, particularly 0.35 to dl / g. In the range of 0.6 dl / g, N,
When measured at 30 ° C. using an N-dimethylformamide solvent, 0.3 to 0.9 dl / g, particularly 0.4 to 0.9 dl / g.
Those having a range of 0.75 dl / g are preferable because a resin composition having excellent flame retardancy, impact resistance, and moldability can be obtained.

Among the thermoplastic resins (A), examples of the polyamide resin include a ring-opened 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), the polycarbonate resin is obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The aromatic homo or copolycarbonate resin has a viscosity average molecular weight in the range of 10,000 to 1,000,000. 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.

Among the above-mentioned thermoplastic resins (A), the polyester resins are essentially polycondensates of dicarboxylic acids and glycols, ring-opening polymers of cyclic lactones, polycondensates of hydroxycarboxylic acids, and dibasic acids. And a glycol polycondensate.

As dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid,
Examples of glycols such as oxalic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, and methyl esters thereof include ethylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, and 1,4-cyclohexanedicarboxylic acid. Examples include methanol and bisphenol A.

Specifically, polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, polycyclohexane dimethylene terephthalate resin, and polyethylene-terephthalate resin
In addition to 1,2-bis (phenoxy) ethane-4,4'-dicarboxylate resin, etc., polyethylene isophthalate / terephthalate resin, polybutylene terephthalate / isophthalate resin, polybutylene terephthalate / decane dicarboxylate resin and polyethylene terephthalate / Polycyclohexane dimethylene terephthalate resin and other copolymers and mixtures. Particularly preferred polyester resins for the present invention include one or more selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyethylene terephthalate / polycyclohexane dimethylene terephthalate resin. And more preferably polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, and polyethylene terephthalate / polycyclohexane dimethylene terephthalate resin.

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

In particular, in the present invention, (A) the thermoplastic resin is (A-1) a thermoplastic resin other than the polyester and (A-1)
-2) When a mixture of polyester resins is used, it is excellent in flame retardancy and mechanical properties, and can be preferably used. (A-1) Thermoplastic resin other than polyester and (A
-2) The mixing ratio of the polyester resin is 1 to 99% by weight:
99-1% by weight, preferably 50-99% by weight:
It is 50 to 1% by weight, more preferably 60 to 95% by weight: 40 to 5% by weight, particularly preferably 70 to 90% by weight: 30 to 10% by weight.

In this case, as the polyester resin (A-2), the above-mentioned polyester resins can be used, but polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, ethylene terephthalate / cyclohexane are preferable. One or more selected from dimethylene terephthalate copolymers can be mentioned, and more preferred are polyethylene terephthalate (PET) resin and ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer. Among them, ethylene terephthalate /
A cyclohexane dimethylene terephthalate copolymer can be particularly preferably used.

The modified phenolic resin (B) used in the present invention is represented by the following general formula (1).

Embedded image (In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms.
R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. )

The structure of the above formula (1) will be described. In the above formula, R ¹ represents an arbitrary organic residue having 1 to 10 carbon atoms, and preferably includes an alkyl group, an aryl group, a glycidyl group, and —C (＝ O) R. Where R is carbon number 1
-9 represents an alkyl group or an aryl group. That is, a phenolic resin obtained by etherifying or esterifying a phenolic hydroxyl group can be preferably used. R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The method for producing the modified phenolic resin represented by the above formula (1) is not particularly limited. For example, as a method for producing an etherified modified phenolic resin, a novolak type, a resol type, and a thermal reaction type are used. A method in which a phenolic resin is reacted with an alkyl halide, epihalohydrin, or the like in the presence of a basic catalyst to produce a phenolic resin. Examples of a method for producing an esterified modified phenolic resin include a method of reacting a novolak-type, resol-type, and heat-reaction-type phenolic resin with an optional acid halide or acid anhydride.

No particular limitation is imposed on the phenolic resin, and commercially available phenolic resins such as novolak type, resol type and heat-reactive type can be used. The novolak type is preferred in view of flame retardancy and fluidity. Can be used. As a method for producing a novolak-type phenol resin, the molar ratio of phenols to aldehydes is 1: 0.
The reaction tank is charged at a ratio of 7 to 1: 0.9, and after adding a catalyst such as oxalic acid, hydrochloric acid, sulfuric acid, and toluenesulfonic acid, the mixture is heated and refluxed for a predetermined time. Vacuum dehydration or static dehydration to remove generated water, and further, a method of removing 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.

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 two or more of these aldehydes can be used as necessary.

Among the modified phenolic resins represented by the general formula (1), modified phenolic resins etherified with a glycidyl group represented by the following general formula (2) are particularly flame-retardant and light-resistant. It can be used preferably in terms of surface.

Embedded image (In the above formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

The molecular weight of the modified phenolic resin is not particularly limited, but is preferably 200 to 2.0 in number average molecular weight.
00, and particularly those in the range of 400 to 1,500 are preferable because of their excellent mechanical properties, fluidity and economy. The modified phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a polystyrene standard sample.

The above modified phenolic resins can be used alone or in combination of two or more as required.

[0070] The shape is not particularly limited.
Any of granules, flakes, powders, needles, and liquids can be used.

(B) The added amount of the modified phenolic resin is
Usually 0.1 parts by weight based on 100 parts by weight of the thermoplastic resin (A).
-20 parts by weight, preferably 1-15 parts by weight, more preferably 2-10 parts by weight. When the amount of the modified phenolic resin (B) is less than 0.1 part by weight, a high flame retardancy-imparting effect cannot be obtained, which is not preferable. If the amount exceeds 20 parts by weight, the impact resistance is reduced and the surface appearance of the molded product is impaired, which is not preferable.

In the present invention, the thermoplastic resin (A) is a thermoplastic resin other than the polyester (A-1) 50 to 99.
% By weight and (A-2) a mixture of 50 to 1% by weight of a polyester resin, (A-2) a polyester resin,
(B) By the combination of the modified phenolic resin represented by the general formula (1) and the (C) phosphorus-based flame retardant, (A-
1) It has been found that the flame retardancy of thermoplastic resins other than polyester is specifically improved.

Accordingly, a resin composition comprising a polyester resin, a modified phenolic resin represented by the general formula (1) and a phosphorus-based flame retardant can be used as a flame retardant for thermoplastic resins other than polyester.

In this case, the polyester resin (A-2) is preferably a polyethylene terephthalate resin,
One or more selected from polypropylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer, more preferably polyethylene terephthalate (PET) resin, ethylene It is a terephthalate / cyclohexane dimethylene terephthalate copolymer.
Among them, ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer can be particularly preferably used from the viewpoint of impact strength and flame retardancy.

As (B) the modified phenolic resin represented by the general formula (1), a modified phenolic resin represented by the general formula (2) can be preferably used.

The (C) phosphorus-based flame retardant used in the present invention is not particularly limited as long as it is an organic or inorganic compound containing phosphorus. Examples thereof include ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate and phosphinate. Phosphine oxide and the like. Among them,
Polyphosphazenes and phosphates are preferred, with aromatic phosphates being particularly preferred.

Among the phosphorus-based flame retardants (C) used in the present invention, the aromatic phosphate is represented by the following general formula (3).

Embedded image

First, the structure of the flame retardant represented by the formula (3) will be described. In the formula (3), n is an integer of 0 or more, and may be a mixture of different n. Also, k, m
Is an integer of 0 or more and 2 or less, respectively, and k + m
Is an integer of 0 or more and 2 or less, preferably, k and m are each an integer of 0 or more and 1 or less, particularly preferably k and m are each 1.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted by halogen-free organic residues. Specific examples include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group.A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferred. Particularly, a phenyl group, a tolyl group and a xylyl group are preferred.

[0080] Further, in the X of formula (3), R ⁴ ~
R ¹¹ represents the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
Examples thereof include an tert-butyl group, and a hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen is particularly preferable. Y is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , C
H ₂ represents CHPh, and Ph represents a phenyl group.

The amount of the aromatic phosphate to be used is generally 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin (A).

Further, the flame-retardant resin composition of the present invention may further comprise (D) a fluorine-based resin and / or a silicone-based compound to suppress the spread of fire during combustion, the suppression of the amount of heat generated during combustion, and the liquid during combustion. The effect of suppressing the drop (drip) of the droplet and improving the heat resistance can be provided.

Examples of such a fluororesin include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, Examples include a tetrafluoroethylene / ethylene copolymer, a (hexafluoropropylene / propylene) copolymer, a polyvinylidene fluoride, and a (vinylidene fluoride / ethylene) copolymer. Among them, polytetrafluoroethylene, (tetra (Fluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride Preferred, in particular polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

The silicone compound means a silicone resin and / or a silicone oil.

The silicone resin used in the present invention is:
A chemically bonded siloxane unit selected from units represented by the following general formulas (4) to (7) and a mixture 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 an allyl group), and preferably has a viscosity of about 200 to 300,000,000 centipoise at room temperature, and is the above-mentioned silicone resin. As long as it is not limited thereto.

[0086]

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The silicone oil used in the present invention is represented by the following general formula (8) (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
A viscosity of 5 to 100,000 centistokes is preferred, but is not limited to the above silicone oil.

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In the present invention, a silicone resin and / or silicone oil can be used as the silicone compound. However, flame retardancy, heat resistance, bleed-out resistance, contact contamination resistance, and deterioration of electrical properties after wet heat treatment. In view of the above, a silicone resin is preferable.

The amount of (D) the fluorine-based resin and / or the silicone-based compound to be added is 100% of the thermoplastic resin (A).
0.01 to 3 parts by weight, preferably 0.1 to 3 parts by weight, per part by weight.
It is 0.5 to 2 parts by weight, more preferably 0.1 to 1 part by weight.

Further, the flame-retardant resin composition of the present invention may contain, if necessary, glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastenite, glass flake, glass beads, talc, mica. And fillers such as clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide. Among them, glass fiber, carbon fiber, and metal fiber can be preferably used, and carbon fiber is most preferably used. The type of these fibrous fillers is not particularly limited as long as they are generally used for reinforcing a resin, and for example, it is possible to select and use a chopped strand of a long fiber type or a short fiber type, a milled fiber, or the like. it can.

The surface of the fibrous, powdery, granular or plate-like filler used in the present invention may be a known coupling agent (for example, a silane coupling agent or a titanate coupling agent), or the like. It can be used after being treated with another surface treating agent.

Glass fiber and carbon fiber are ethylene /
It may be coated or bundled with a thermoplastic resin such as a vinyl acetate copolymer or a thermosetting resin such as a polyurethane resin or an epoxy resin.

Further, as long as the object of the present invention is not impaired, an antioxidant such as a hindered phenol-based, phosphorus-based or sulfur-based antioxidant, a heat stabilizer, an ultraviolet absorbing agent may be added to the flame retardant resin composition of the present invention. Agents (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.),
Lubricants and release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and ethylene wax, etc.), coloring inhibitors (phosphites, hypophosphites, etc.), nucleating agents, Plasticizer,
Flame retardants, antistatic agents, and coloring agents including dyes and pigments (cadmium sulfide, phthalocyanine, titanium oxide, etc.)
One or more ordinary additives such as the above can be added.

The flame-retardant resin composition of the present invention is usually produced by a known method. For example, a thermoplastic resin (A), a modified phenolic resin (B), a phosphorus-based flame retardant (C) and other necessary additives are supplied to an extruder or the like with or without pre-mixing, and then heated to 150 ° C. It is prepared by sufficiently melting and kneading in a temperature range of -350 ° C. In this case, for example, a single-screw extruder, a twin-screw extruder, a kneader of a kneader type or the like equipped with a “unimelt” type screw can be used. It is preferable to use several elements by inserting or not inserting them.

The thermoplastic resin composition of the present invention is excellent not only in flame retardancy, but also in mechanical properties, heat resistance, retention stability and moldability, and can be melt-molded, so that it can be extruded, injection-molded and press-molded. It can be formed into a film, a tube, a rod, or a molded product having any desired shape and size. Furthermore, by utilizing the flame retardancy, it can be used for various applications such as housings for electric / electronic parts, automobile parts, mechanical mechanism parts, OA equipment, home electric appliances and the like and parts thereof.

For example, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors,
Variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal, FDD carriage, FDD Chassis, motor brush holder, parabolic antenna,
Electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment such as audio laser disks (registered trademark) and compact disks Parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, household and office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs , Oil-less bearings, stern bearings, underwater bearings, etc., various motor-related parts, machinery-related parts such as lighters and typewriters, optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machinery-related Parts; alternator terminal, alternator -Various valves such as connectors, IC regulators, exhaust gas valves, various fuel-related / exhaust / intake systems pipes, air intake nozzle snorkels, intake manifolds, fuel pumps, engine cooling water joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, Cooling water sensor, oil temperature sensor, brake pad wear sensor,
Throttle position sensor, crankshaft position sensor, air flow meter, 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 switcher, starter switch , Starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate,
Step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, personal computer, printer, display, CRT
Display, fax, copy, word processor, notebook computer, mobile phone, PHS, DVD drive, PD drive, flexible disk drive, etc., housing for storage device, chassis, relay, switch, case member, transformer member, coil bobbin, etc. It is useful for equipment parts, automobile parts, machine parts, and other various uses.

[0097]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. In addition, the number of parts and% in an Example show a weight part and weight%, respectively.

Reference Example 1 (A) Thermoplastic resin resin <A-1> Graft (co) polymer A method for preparing a 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 (approximately 10
0 × 10 3 m / s 2)) After 30 minutes of centrifugation, insolubles were filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured. Graft rate = [(n)-(m) x L] / [(m) x 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 and then dried to obtain a powder. The graft ratio of the obtained graft copolymer was 36%, and it contained 18.1% of a non-graft copolymer composed of 70% of styrene structural units and 30% of acrylonitrile. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.34 dl / g.

<A-2> Preparation of vinyl copolymer <A-2-1> Styrene 70%, acrylonitrile 30
% Of a monomer mixture was subjected to suspension polymerization to prepare a vinyl copolymer <A-2-1>. The obtained vinyl copolymer <A-2-1> had a limiting viscosity of 0.53 dl / g of a methyl ethyl ketone-soluble component. <A-2-2> Vinyl copolymer obtained by suspension polymerization of a monomer mixture composed of 69.7% of styrene, 30% of acrylonitrile, and 0.3% of glycidyl methacrylate.
2> was prepared. Obtained vinyl copolymer <A-2-
2> is the intrinsic viscosity of the soluble portion of methyl ethyl ketone is 0.54
dl / g. <A-2-3> Styrene 51%, acrylonitrile 9
%, And a monomer mixture composed of 40% of N-phenylmaleimide was solution-polymerized in a cyclohexanone solvent to prepare a vinyl copolymer <A-2-3>. The intrinsic viscosity of the obtained vinyl copolymer <A-2-3> was 0.59 dl / g.

<A-3> Polyethylene terephthalate resin A polyethylene terephthalate resin having an intrinsic viscosity of 0.65 (a mixed solvent of phenol / tetrachloroethane of 1: 1 at 25 ° C.) was used. <A-4> Ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer (PET / PCT copolymer) "Easter GN071" (manufactured by Eastman) was used. <A-5> Polybutylene terephthalate resin Toray PBT1100S (Toray) was used. <A-6> A polycarbonate resin “Iupilon S3000” (manufactured by Mitsubishi Engineering-Plastics Corporation) was used. <A-7> Polyamide 6 resin "Amilan CM1017" (manufactured by Toray Industries, Inc.) was used.

Reference Example 2 Modified phenolic resin <B-1> A glycidyl group-modified novolak phenolic resin "EPPN-201-H" (manufactured by Nippon Kayaku Co., Ltd.) represented by the following formula (9) was used.

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<B-2> As a comparative example, the following formula (10)
"Sumilite Resin PR53195" (manufactured by Sumitomo Durres Co., Ltd.) which is an unmodified novolak phenol resin represented by

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Reference Example 3 (C) Phosphorus-based flame retardant <C-1> An aromatic bisphosphate "PX-200" (manufactured by Daihachi Chemical Co., Ltd.) represented by the following formula (11) was used.

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Reference Example 4 (D) Fluorine-based resin and / or silicone-based compound <D-1> Polytetrafluoroethylene, polyfuron F201 (manufactured by Daikin Industries, Ltd.) was used. <D-2> “DC4-7081” which is a silicone resin
(Manufactured by Toray Dow Corning Silicone Co., Ltd.). Reference Example 5 Glass fiber (abbreviated as GF in Table 2) "CS3PE941S" (manufactured by Nitto Boseki) was used.
In addition, when mix | blending a glass fiber, it mix | blended so that the glass fiber weight% in a resin composition might be 30%.

[Examples 1 to 16 and Comparative Examples 1 to 17] The thermoplastic resin (A), modified phenolic resin (B), phosphorus-based flame retardant (C) and other necessary additives prepared in Reference Examples Was mixed at the mixing ratio shown in the table, and 30 mmφ with vent
Using a twin screw extruder (PCM-30, manufactured by Ikegai Iron Works)
A pellet-shaped polymer was produced by melt-kneading and extruding at 220 to 270 ° C. Next, each test piece was molded with an injection molding machine (promat 40/25, manufactured by Sumitomo Heavy Industries, Ltd.) at an injection pressure of the lower limit pressure +1 MPa, and the physical properties were measured under the following conditions.

(1) Flame retardancy: 1.6 obtained by injection molding
The flame retardancy of five test pieces was evaluated in accordance with the evaluation standard defined in UL94 for the test pieces for flame retardancy evaluation having a thickness of 0.8 mm or 0.8 mm. Flame retardant level is V
−0>V−1>V−2> HB. (2) Impact resistance: Impact resistance was evaluated according to ASTM D256-56A. (3) Heat resistance: ASTM D648 (Load: 1.82M)
Heat resistance was evaluated according to Pa). (4) Light fastness: Using a xenon light fastness tester Ci35W type (manufactured by Atlas), 55 ° C., 0.7 W / m ² , filter (inner: quartz, outer: soda lime) 10
Irradiated for 0 hours. The hue before and after irradiation was measured with a hue color difference meter (manufactured by Suga Test Instruments Co., Ltd.), and ΔΔE * (= ΔE *-after irradiation)
ΔE *) before irradiation was determined. The smaller the ΔΔE *, the better the light resistance.

The measurement results of the flame retardancy, impact resistance, heat resistance and light resistance of each sample are summarized in Tables 1, 2 and 3.

[0109]

[Table 1]

From the measurement results of Examples 1 to 7 and Comparative Examples 1 to 11, the modified phenolic resin <B-1> of the present invention was added to the ABS resin together with the phosphorus-based flame retardant <C-1>. This shows that a resin composition having improved flame retardancy and good impact resistance, heat resistance, and light resistance can be obtained.

From the comparison of Examples 1 to 5, when a mixture of ABS resin and polycarbonate resin is used as the thermoplastic resin, higher flame retardancy can be imparted, and impact resistance and heat resistance are improved. You can see that. ABS resin and polyester resin (PET,
It is understood that a higher degree of flame retardancy can be obtained when a mixture of PET / PCT and PBT) is used. In particular, a mixture of ABS resin and PET resin, or a mixture of ABS resin and PET / PCT resin provides the highest rank flame retardancy, and especially when PET / PCT resin is used, a resin composition having excellent mechanical properties. It turns out that a thing is obtained.

Therefore, it is understood that the resin composition comprising the polyester and the modified phenolic resin functions as a flame retardant for the ABS resin. Particularly when a PET resin or a PET / PCT resin is used as the polyester resin, specifically high flame retardancy can be imparted.

As can be seen from the sixth embodiment, ABS
By using a vinyl copolymer in which a part of the resin is modified with an epoxy group, the flame retardancy is further improved and the impact resistance is greatly improved. Further, from Example 7, it can be seen that not only the heat resistance is improved but also the burning time can be shortened by using a vinyl copolymer in which a part of the ABS resin is modified with a maleimide group.

On the other hand, no flame retardancy was obtained only by adding a phosphorus-based flame retardant to the ABS resin (Comparative Example 1). Similarly, when a mixture of the ABS resin and each resin was used, the phosphorus-based flame retardant was similarly added. Alone does not provide flame retardancy (Comparative Examples 2 to 7). In addition, when an unmodified phenol resin is used (Comparative Examples 8 to 11), although the flame retardancy is improved, the effect is small and the light resistance is significantly reduced.

[0115]

[Table 2]

From the comparison of the measurement results of Examples 8 to 12 and Examples 1 to 5, it was found that the addition of a fluorine-based resin or a silicone-based compound to the resin composition of the present invention makes it possible to achieve a higher degree of difficulty with a reduced burning time. It can be seen that flammability can be imparted.

[0117]

[Table 3]

From the comparison of the measurement results of Examples 13 to 16 and Comparative Examples 12 to 17, even when a polyester resin (PET, PBT) or a polyamide resin was used as the thermoplastic resin, the phosphorus-based flame retardant <C-1> was used. It is also found that by adding the modified phenolic resin <B-1> of the present invention, a resin composition having improved flame retardancy and good impact resistance, heat resistance and light resistance can be obtained. In the case of a nylon resin, a polyester resin, an epoxy-modified phenolic resin and an aromatic phosphate are blended (Example 1).
According to 6), it can be seen that a high degree of flame retardancy can be imparted.

On the other hand, polyester resins (PET, PB
T) or the addition of a phosphorus-based flame retardant to a polyamide resin alone does not provide flame retardancy (Comparative Examples 12, 14, 16, 1)
7). When the unmodified phenolic resin was used (Comparative Examples 13 and 15), it was found that sufficient flame retardancy was not obtained, and that the light resistance was significantly reduced.

[0120]

The resin composition of the present invention exhibits excellent flame retardancy without impairing the mechanical properties of the thermoplastic resin, and is particularly excellent in light resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/14 C09K 21/14 // (C08L 101/00 (C08L 101/00 61:14) 61:14 ) F-term (Reference) 4F071 AA01 AA41 AB05 AC15 AE07 AH05 AH07 AH12 AH17 BB03 BB05 BB06 4H028 AA35 AA36 BA06 4J002 AA011 BC021 BC061 BD153 BN151 CC092 CD001 CD072 CF001 CF061 GW001 CG001 CG001 GW 146

Claims (17)

[Claims] 1. (B) 0.1 to 20 parts by weight of a modified phenolic resin represented by the following general formula (1) and (C) a phosphorus-based resin per 100 parts by weight of a thermoplastic resin Flame retardant 1
A flame-retardant resin composition containing up to 30 parts by weight. Embedded image (In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms.
R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) 2. The flame-retardant resin composition according to claim 1, wherein the modified phenolic resin (B) is a modified phenolic resin represented by the following general formula (2). Embedded image (In the above formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) 3. The flame-retardant resin composition according to claim 1, wherein (C) the phosphorus-based flame retardant is an aromatic phosphate represented by the following general formula (3). Embedded image (In the above formula, R ^{4 to} R ¹¹ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
r ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Y is a direct bond, O, S, S
O ₂ , C (CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group. Further, n is an integer of 0 or more, and may be a mixture of different n. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. ) 4. The flame-retardant resin composition according to claim 1, wherein (A) the thermoplastic resin is a polystyrene resin. 5. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyester resin. 6. A thermoplastic resin comprising 1 to 99% by weight of a polycarbonate resin and 99 to 1% by weight of a polystyrene resin.
The flame-retardant resin composition according to any one of claims 1 to 3, which is a mixture by weight. 7. The thermoplastic resin (A) comprises 1 to 99% by weight of a thermoplastic resin other than the polyester (A-1) and (A-2)
The flame-retardant resin composition according to any one of claims 1 to 3, which is a mixture of 99 to 1% by weight of a polyester resin. 8. The flame-retardant resin composition according to claim 7, wherein the thermoplastic resin other than (A-1) polyester is a polystyrene resin. 9. A polystyrene resin containing an epoxy group-modified vinyl copolymer.
The flame-retardant resin composition according to the above. 10. The flame-retardant resin composition according to claim 8, wherein the polystyrene-based resin contains a maleimide group-modified vinyl-based copolymer. 11. (A-2) The polyester resin is a polyethylene terephthalate resin and / or a copolymer containing ethylene terephthalate units.
0. The flame-retardant resin composition according to any one of 0. 12. The flame-retardant resin composition according to claim 11, wherein (A-2) the polyester resin is an ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer. 13. A polyester resin, represented by the following general formula (1)
A flame retardant comprising a modified phenolic resin represented by the formula and a phosphorus-based flame retardant. Embedded image (In the above formula, R ¹ represents an organic residue having 1 to 10 carbon atoms.
R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) 14. A polyester resin, represented by the following general formula (2)
A flame retardant comprising a modified phenolic resin represented by the formula and a phosphorus-based flame retardant. Embedded image (In the above formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) 15. The flame retardant according to claim 13, wherein the polyester resin is a polyethylene terephthalate resin and / or a copolymer containing polyethylene terephthalate units. 16. The flame retardant according to claim 13, wherein the polyester resin is an ethylene terephthalate / cyclohexane dimethylene terephthalate copolymer. 17. A molded article comprising the flame-retardant resin composition according to claim 1.