JP2000103973A - Flame-retardant resin composition and molding product comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of providing high flame retardance, developing excellent mechanical characteristics, impact resistance, fluidity, or the like, by mixing a thermoplastic resin with a specific phosphorus compound. SOLUTION: This composition comprises (A) 100 pts.wt. of a thermoplastic resin (preferably a polystyrene-based resin, a polyester resin, a polybutylene terephthalate, or the like), (B) 5-40 pts.wt. of a phosphorus compound of formula I (R1 and R2 are each an alkyl, an aryl, an alkoxy, an aryloxy or R1 and R2 mutually form a ring) (preferably a phosphorus compound of formula II) and (C) 1-30 pts.wt. of a phenol-based resin. Preferably, the composition is further mixed with 1-30 pts.wt. of a fluororesin. More preferably, the composition is further mixed with 1-30 pts.wt. of an aromatic phosphate of formula III [X is a group of formula IV (R1 to R4 are each H or a 1-5C alkyl) or the like; Ar1 to Ar4 are each phenyl or the like; (k) and (m) are each 0-2 and k+n is 0-2].

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 without impairing the mechanical properties (impact resistance, rigidity, heat resistance) inherent in the thermoplastic resin.

[0002]

2. Description of the Related Art Plastics have excellent mechanical properties,
Due to its moldability and electrical insulation, it is used in a wide range of fields including home electric appliances, OA appliances, automobiles and other parts. However, most of plastics are flammable, and various techniques have been proposed for flame retardancy due to safety issues.

[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.

[0005] As a method of making a thermoplastic resin flame-retardant without using a chlorine or bromine-based flame retardant, ammonium polyphosphate and pentaerythritol are added to a rubber-reinforced polystyrene resin.
A method of blending a polyhydroxy compound such as benzene and a silane coupling agent (JP-A-5-140412),
A method of blending a melamine-coated ammonium polyphosphate and a specific nitrogen-containing organic compound with a thermoplastic resin (JP-A-6-34)
No. 0815) and a method of blending a small amount of a phenol resin and a flame retardant in a thermoplastic resin (Japanese Patent Application Laid-Open No. 7-53879).

[0006]

Problems to be Solved by the Invention
The composition described in Japanese Patent Publication No. 2 cannot obtain sufficient flame retardancy, and furthermore, when the mechanical properties are reduced or a polyhydric alcohol compound is used, mold contamination during molding or stickiness due to moisture absorption of the molded product occurs. Had problems. Also, JP-A-6-3408
The compositions described in JP-A No. 15 and JP-A-7-53879 have a problem that a sufficient flame retardancy cannot be obtained with a styrene resin.

[0007] It is an object of the present invention to solve the above problems and to provide a resin composition which imparts high flame retardancy to a thermoplastic resin and has excellent mechanical properties, heat resistance and fluidity.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present invention can impart specific flame retardancy by blending a specific phosphorus compound into a thermoplastic resin,
In addition, they have been found to be excellent in mechanical properties, impact resistance, and heat resistance.

That is, the present invention relates to "(A) 100 parts by weight of a thermoplastic resin, (B) 5 to 30 parts by weight of a phosphorus compound represented by the following general formula (1), (C) phenolic resin 1 A flame-retardant resin composition containing up to 30 parts by weight.

[0010]

Embedded image (R ¹ and R ² are the same or different groups selected from an alkyl group, an aryl group, an alkoxy group and an allyloxy group, and R ¹ and R ² may form a ring with each other.) .

[0011]

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 which can be molded by utilizing this.

Specific examples thereof include polystyrene resins, polystyrene resins such as styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer (ABS resin), polyester resins, liquid crystal polyester resins, polycarbonate resins, polyamide resins, and the like. Resin, polyphenylene oxide resin, modified polyphenylene oxide resin, polyphenylene sulfide resin, polyoxymethylene resin, phenoxy resin, polypropylene resin, polyolefin resin such as polyethylene, ethylene / propylene resin, ethylene / 1-butene resin,
Ethylene / propylene / non-conjugated diene resin, ethylene /
Ethyl acrylate resin, ethylene / glycidyl methacrylate resin body, ethylene / vinyl acetate / glycidyl methacrylate resin, ethylene / vinyl acetate / glycidyl methacrylate resin, ethylene / propylene-g-maleic anhydride resin, polyester polyether elastomer, polyester Elastomers such as polyester elastomers,
Alternatively, a mixture of two or more of these thermoplastic resins may be mentioned, and polystyrene resins such as a polystyrene resin, a styrene / acrylonitrile copolymer, and an acrylonitrile / butadiene / styrene copolymer (ABS resin);
Modified polyphenylene oxide resin, polyester resin,
Polyamide resin, polycarbonate resin, phenoxy resin, one or a mixture of two or more selected from polyphenylene sulfide resin is preferable, more preferably,
One or more selected from polystyrene resins such as polystyrene resins, styrene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene copolymers (ABS resins), modified polyphenylene oxide resins, polyester resins, polyamide resins, polycarbonate resins, and phenoxy resins; It is a mixture of two or more.

Among the above-mentioned thermoplastic resins (A), the polyester resin is essentially a polycondensate of dicarboxylic acid and glycol, a ring-opening polymer of cyclic lactone, a polycondensate of hydroxycarboxylic acid, and a dibasic acid. 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, and more preferably polybutylene terephthalate (PBT) 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.

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), aliphatic-aromatic polyamides such as poly (hexamethylene isophthalamide) (hereinafter abbreviated as 6I), poly (tetramethylene isophthalamide) (hereinafter abbreviated as 4I), and copolymers thereof. Mixtures can be mentioned. Particularly, polyamides suitable for the present invention include nylon 6, nylon 66, nylon 6/66 copolymer, and nylon 66 / 6T copolymer.

Although the molecular weight of such a polyamide resin is not particularly limited, it can be usually used in 98% sulfuric acid, a concentration of 1%, and a relative viscosity of 1.7 to 4.5 measured at 25 degrees. Preferably, it is 2.0 to 4.0, particularly preferably 2.0 to 3.5.

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). Oxide resin).

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

Examples of such a rubber-modified styrene resin include impact-resistant polystyrene, ABS resin and 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 a styrene monomer is grafted to a rubbery polymer, and another having a structure containing a styrene monomer (co) It includes those having a structure in which the polymer is not grafted to the rubbery polymer.

Specifically, the rubbery polymer is obtained by graft polymerization of 95 to 20 parts by weight of a monomer or monomer mixture containing 20% by weight or more of an aromatic vinyl monomer to 5 to 80 parts by weight of a rubbery polymer. (A1) obtained by polymerizing a monomer or monomer mixture containing 5 to 100% by weight of the obtained graft (co) polymer and 20% by weight or more of an aromatic vinyl monomer.
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 preferred, 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.

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 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).

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

As monomers other than the aromatic vinyl monomers, vinyl cyanide monomers are used for the purpose of further improving impact resistance, and (meth) acrylic monomers are 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.

(A1) The monomer or monomer mixture used in 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-based 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. 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 it is 90 to 30% by weight.

(A1) The ratio of the rubbery polymer to the monomer mixture in obtaining the graft (co) polymer is preferably 100 parts by weight of the total graft copolymer from the viewpoint of the impact resistance of the resin composition. The rubbery polymer is preferably at least 5 parts by weight, more preferably at least 10 parts by weight, and from the viewpoint of the impact resistance of the resin composition and the appearance of the molded product, at most 80 parts by weight,
More preferably, 70 parts by weight or less is used. Also, the monomer or monomer mixture is 95 parts by weight or less, preferably 9 parts by weight.
0 parts by weight or less, 20 parts by weight or more, preferably 30 parts by weight or more.

The (A1) 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.

(A1) 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. The graft ratio of the graft (co) polymer is not particularly limited, but is preferably 20 to 80% by weight, especially 2 to obtain a resin composition having excellent impact resistance and gloss.
5 to 50% by weight is preferred. Here, the graft ratio is calculated by the following equation: graft ratio (%) = <amount of vinyl copolymer graft-polymerized to rubbery polymer> / <rubber content of graft copolymer> × 100.

The properties of the ungrafted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component is 0.25-0.
6 dl / g, especially in the range of 0.25 to 0.5 dl / g,
Since a resin composition having excellent impact resistance can be obtained, it is preferably used.

(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, o-ethylstyrene, and the like, with styrene being particularly 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 as required.

(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 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 bulk polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization.
Conventional methods such as a suspension polymerization method and a solution-bulk polymerization method can be used.

In the present invention, a carboxyl group, a hydroxyl group, an epoxy group, an amino group,
A modified vinyl polymer containing at least one functional group selected from oxazoline groups (hereinafter abbreviated as a modified vinyl polymer) can also be used. The modified vinyl 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,
It is a polymer containing at least one functional group selected from an amino group and an oxazoline group. The content of the compound containing these functional groups is not limited, but is preferably 0.01 to 2 parts by weight per 100 parts by weight of the modified vinyl polymer.
A range of 0% by weight is preferred.

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

Although the properties of the modified vinyl polymer are not limited, the intrinsic viscosity [η] (methyl ethyl ketone solvent, 30 ° C.
Measurement) is 0.2 to 0.65 dl / g, especially 0.35 to
In the range of 0.6 dl / g, an N, N-dimethylformamide solvent at a temperature of 30 ° C.
A resin composition in the range of 0.9 dl / g, particularly 0.4 to 0.75 dl / g is preferable because excellent flame retardancy, impact resistance and moldability can be obtained.

The phosphorus compound (B) of the present invention is a compound represented by P-
It has an H bond and is represented by the following general formula (1).

[0048]

Embedded image (R ¹ and R ² are the same or different groups selected from an alkyl group, an aryl group, an alkoxy group and an allyloxy group, and R ¹ and R ² may form a ring with each other.) Among the compounds represented by 1), preferably, R
¹ and R ² are the same or different groups selected from an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 24 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an allyloxy group having 6 to 24 carbon atoms. Yes, R ¹ and R ² are They may form a ring with each other.

The following are specific examples.

[0050]

Embedded image Among them, a phosphorus compound represented by the following general formula (2) can be preferably used in terms of flame retardancy.

[0051]

Embedded image PH bonds have higher reactivity than P = O and PO- bonds. Therefore, it easily reacts with the resin during combustion, and the fire extinguishing effect is large. In addition, since the P—H bond also has a high reactivity with olefins (double bonds), the generation of olefins (double bonds) that causes gelation (reduction of MI retention (described below)) when staying is caused. Can be suppressed.

The amount of the phosphorus compound represented by the general formula (1) is usually 5 to 4 with respect to 100 parts by weight of the thermoplastic resin.
0 parts by weight, preferably 6 to 35 parts by weight, more preferably 7 to 30 parts by weight. If the amount used is less than 5 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 40 parts by weight, the mechanical properties deteriorate and the surface appearance is impaired, which is not preferable.

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. Among them, a phenol novolak resin which does not contain a curing agent and is non-thermally reactive is preferred in terms of flame retardancy, impact resistance and economy.

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

The phenolic resin (C) may 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 can be 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 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.

In the case of a resole 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, salicylic acid Methyl,
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 molecular weight of the phenolic resin is not particularly limited, but is preferably 200 to 2,000 in number average, and particularly preferably in the range of 400 to 1,500 is excellent in mechanical properties, moldability and economical efficiency. preferable. The phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a phenol resin standard sample.

In the present invention, when (C) a phenolic resin is blended, 0.1 to 30 parts by weight, preferably 0.2 to 25 parts by weight, more preferably 100 parts by weight of the thermoplastic resin (A). Is 0.5 to 20 parts by weight.
When the blending amount of the (C) phenolic resin is within the above range, the flame retardancy becomes good.

The resin composition of the present invention further comprises (D)
Addition of a fluorine-based resin can suppress dropping (drip) of droplets during combustion, and can impart high flame retardancy. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / 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. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

The amount of the fluororesin (D) is usually 0.01 to 3 parts by weight, preferably 0.1 to 0.1 part by weight, per 100 parts by weight of the thermoplastic resin (A) in order to enhance the flame retardancy of the resin composition. ~
It is 2 parts by weight, more preferably 0.2 to 1 part by weight.

In the present invention, by further blending the aromatic phosphate (E), a high flame retardancy with a further reduced burning time can be imparted and the fluidity can be greatly improved.

The (E) aromatic phosphate used in the present invention is represented by the following formula (6).

[0064]

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, preferably an integer of 1 to 5. (In addition, k and m are each an integer of 0 or more and 2 or less, and k + m is 0 or more and 2 or less.
The following integers are preferred, but k and m are each preferably an integer of 0 or more and 1 or less, and particularly preferably k and m are each 1.

In the formula (3), R ^{3 to} R ¹⁰ represent 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, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-
Butyl group, n-isopropyl, neopentyl, tert
A pentyl group, 2-isopropyl, neopentyl, te
rt-pentyl group, 3-isopropyl, neopentyl,
a tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group and the like.
A methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

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,
Examples include a mesityl group, a naphthyl group, an indenyl group, an anthryl group, and the like. A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

Y is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and 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, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.

In the present invention, (A) a thermoplastic resin and (B) P
The reaction at the time of combustion of the phosphorus compound having a -H bond is promoted, and a resin composition exhibiting excellent flame retardancy with reduced combustion time can be obtained.

Here, (F) a radical generator is a compound which generates carbon radicals by light or heat. Among these radical generators, in order to obtain a high effect as a flame retardant, a melt compound is required. Sometimes, it is preferable to generate a carbon radical upon combustion without generating a carbon radical. Therefore, the radical generator used in the present invention preferably has a one-minute half-life of 200 ° C. or more, and more preferably. Is preferably 250 ° C. or higher.

Here, the one-minute half-life can be measured by a known method. For example, when the radical generator is 0.1
A mol% benzene solution is sealed in a glass ampoule which has been purged with nitrogen, placed in a thermostat set at a predetermined temperature (T), and thermally decomposed. Assuming that the thermal decomposition time at this time is t, the concentration of the decomposed radical generator is X, the initial concentration of the radical generator is a, and the decomposition rate constant is k, ln (a / (ax)) = kt (I) Holds.

Here, since the half-life is the time until the concentration of the radical generator is reduced to half of the initial value due to the generation of radicals, by substituting the relationship of X = a / 2 into the above equation, kt _1/2 = ln2 (II) is obtained.

Accordingly, thermal decomposition is carried out at a certain temperature, the relationship between time t and ln (a / (ax)) is plotted, k is obtained from the slope of the obtained straight line, and t is obtained from the equation (II). _1/2
Can be measured. The above measurements were performed at several temperatures (T), and t _1/2 and 1 / T obtained from each were measured.
Is plotted, and the decomposition temperature at 1 minute half-life can be measured from the obtained straight line.

As such a radical generator, a compound represented by the following general formula (4) is specifically exemplified.

[0075]

Embedded image Here, X represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a carboxyl group, a hydroxyl group, an amino group, a nitrile group, a nitro group, or an epoxy group. N is an integer of 1 to 5.

Among the radical generators represented by the above general formula (4), 2,3-dimethyl-2,3-diphenylbutane represented by the following general formula (5) is preferred in terms of flame retardancy. It can be preferably used.

[0077]

Embedded image The amount of the (F) radical generator used in the present invention is usually 0.0% with respect to 100 parts by weight of the thermoplastic resin (A).
The amount is 1 to 2 parts by weight, preferably 0.02 to 1.5 parts by weight, more preferably 0.03 to 1 part by weight. When the amount is within the above range, it is preferable in terms of flame retardancy.

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.

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, and an ultraviolet absorber can be used in 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) a thermoplastic resin,
(B) A phosphorus compound having a P—H bond and other necessary additives are supplied to an extruder or the like with or without premixing, and sufficiently melt-kneaded in a temperature range of 150 ° C. to 350 ° C. Prepared. 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 and moldability, and can be melt-molded, so that extrusion molding, injection molding, press molding, etc. are possible. 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 parts such as audio, laser disks, and compact disks, and lighting parts , Refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc., household, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings , Stern bearings, underwater bearings, etc., motor parts, mechanical parts such as lighters and typewriters, optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machinery parts; alternator terminals , Alternator connector , IC regulator, various valves such as exhaust gas valve, fuel related, exhaust system, intake system various 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 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, Distributor, Starter switch, Starter relay, Transmission gear Wire harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, 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, floppy disk drive, etc., storage device housing, chassis, relay, switch, case member, transformer member , Electric and electronic equipment parts such as coil bobbins,
Useful for automotive parts, machine parts, and other various applications.

[0083]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. In the examples, the number of parts and% indicate parts by weight and% by weight, respectively, and the unit "" means inches (1 inch = 2.54 cm).

Reference Example 1 (A1) 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 (about 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 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-1>.

The graft ratio of the obtained graft copolymer <A-1> was 36%. This graft copolymer <A
-1> is a non-grafting copolymer composed of 70% of styrene structural units and 30% of acrylonitrile 18.1
%. The intrinsic viscosity of the N, N-dimethylformamide-soluble component was 0.48 dl / g.

Reference Example 2 <A-2> Preparation of vinyl copolymer A vinyl copolymer <A-2> was prepared by suspension polymerization of a monomer mixture composed of 70% styrene and 30% acrylonitrile. . The obtained vinyl copolymer <A-2> is N,
The intrinsic viscosity of the N-dimethylformamide-soluble component is 0.73
Met.

Reference Example 3 <A-3> Modified polyphenylene oxide "Noryl 115" (manufactured by Nippon GE Plastics Co., Ltd.) was used.

<A-4> Polystyrene "Stylon 666" (manufactured by Asahi Kasei Corporation) was used.

<A-5> Polycarbonate "Iupilon S3000" (manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) is 50% by weight and ABS is "TOYOLAC T".
-100 "(manufactured by Toray Industries, Inc.) with a 50% by weight vented 30 mm φ twin screw extruder (manufactured by Ikegai Iron Works, PCM-3
Using 0), the mixture was melt-kneaded at 280 ° C. and extruded to produce a pelletized polycarbonate / ABS (50/50) alloy.

<A-6> Polybutylene terephthalate "Toray PBT1100S" (manufactured by Toray Industries, Inc.) was used.

<A-7> Polyamide 6 "Amilan CM1010" (manufactured by Toray Industries, Inc.) was used.

Reference Example 4 (B) Phosphorus compound having a P—H bond <B-1> The phosphorus compound “HCA” of the above formula (2) (manufactured by Sanko Chemical Co., Ltd.) was used. <B-2> Diphenyl phosphite (reagent) was used.

Reference Example 5 (C) Phenolic Resin <C-1> A non-thermally reactive phenol novolak resin having a number average molecular weight of 700, PR53195 (Sumitomo Durez Co., Ltd.) was used.

Reference Example 6 (D) Fluorine Resin <D-1> Polytetrafluoroethylene, polyfuron F201 (manufactured by Daikin Industries, Ltd.) was used.

Reference Example 7 (E) Aromatic phosphate <E-1> An aromatic bisphosphate PX-200 (manufactured by Daihachi Chemical Co., Ltd.) represented by the following formula (6) was used.

[0098]

Embedded image Reference Example 8 (F) Radical generator <F-1> 2,3-diphenyl-2,3-dimethylbutane "Nofmer BC" (manufactured by NOF CORPORATION) was used (1 minute half-life temperature: 330 ° C).

Examples 1-21 and Comparative Examples 1-21 (A) a thermoplastic resin, (B) a phosphorus compound having a PH bond, (C) a phenolic resin and other additives prepared in Reference Examples Were mixed at the mixing ratios shown in Tables 1 to 4, and a vented 30 mmφ twin-screw extruder (PCM, manufactured by Ikegai Iron Works, Ltd.)
Using -30), melt-kneading and extrusion were performed to produce a pellet-shaped polymer. 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: 1/1 obtained by injection molding
Five test pieces were evaluated for flame retardancy in accordance with the evaluation criteria defined in UL94 for the 6 "thickness flame retardant test specimens. The flame retardancy level was V-0>V-1> V-2. >
It decreases in the order of HB.

(2) Mechanical properties: The tensile yield strength of a dumbbell specimen obtained by injection molding was measured in accordance with ASTM D-638.

(3) Izod impact strength: ASTM D
The impact resistance was evaluated according to 256-56A.

(4) Deflection temperature under load: ASTM D64
8 (load: 1.82 MPa).

(5) Fluidity: Using a melt indexer (manufactured by Toyo Seiki Co., Ltd.), the outflow MI value (g / 10 minutes) for 10 minutes under the temperature and load conditions shown in the table was measured.
The larger the MI value, the better the fluidity.

The results of measurement of the flame retardancy, mechanical properties, impact resistance, heat resistance and fluidity of each sample are summarized in Tables 1 to 8.

[0106]

[Table 1] From the measurement results of Examples 1 to 5 and Comparative Examples 1 to 5, the flame retardancy was obtained by adding a phosphorus compound having a P—H bond to the ABS resin and a phenolic resin together in an amount within the range of the present invention. It can be seen that a resin composition having improved mechanical properties, impact resistance and heat resistance can be obtained.

Further, by adding a fluorine-based resin, it is possible to impart a high degree of flame retardancy while suppressing dripping during combustion.

Further, it can be seen that when an aromatic phosphate is used in combination, the burning time is shortened, the flame retardancy is further improved, and the fluidity is improved.

Further, by using a radical generator together, the burning time can be shortened.

On the other hand, when only a phosphorus compound having a PH bond was added to an ABS resin (Comparative Example 1), when only a phenolic resin was added (Comparative Example 2), an aromatic compound having no PH bond was added. It can be seen that when only the aromatic phosphate is added (Comparative Example 3) and when only the aromatic phosphate and the phenolic resin are used together (Comparative Example 4), sufficient flame retardancy cannot be obtained.

[0111]

[Table 2]

[0112]

[Table 3] From the measurement results of Examples 5 to 21 and Comparative Examples 5 to 21, AS
The resin, modified polyphenylene oxide resin, polystyrene resin, polycarbonate / ABS alloy, PBT, and nylon 6 are difficult to use together with a phosphorus compound having a P—H bond and a phenolic resin in the amounts used within the range of the present invention. It is understood that a resin composition having improved flammability and excellent mechanical properties, impact resistance and heat resistance can be obtained.

Further, by adding a fluorine-based resin, it is possible to impart a high degree of flame retardancy while suppressing dripping during combustion.

It can also be seen that when aromatic phosphate is used in combination, the burning time is shortened, the flame retardancy is further improved, and the fluidity is improved.

Further, by using a radical generator together, the burning time can be shortened.

[0116]

The resin composition of the present invention exhibits excellent flame retardancy without impairing the mechanical properties of the thermoplastic resin.

Claims (11)

[Claims] (A) a phosphoric compound represented by the following general formula (1):
A flame-retardant resin composition containing 0 parts by weight and (C) 1 to 30 parts by weight of a phenolic resin. Embedded image (R ¹ and R ² are the same or different groups selected from an alkyl group, an aryl group, an alkoxy group and an allyloxy group, and R ¹ and R ² may form a ring with each other.) 2. The flame-retardant resin composition according to claim 1, wherein the phosphorus compound (B) has the following general formula (2). Embedded image 3. The flame-retardant resin composition according to claim 1, further comprising (D) 0.01 to 3 parts by weight of a fluororesin based on 100 parts by weight of the thermoplastic resin (A). . 4. The composition according to claim 1, further comprising (E) 1 to 30 parts by weight of an aromatic phosphate represented by the following general formula (3) per 100 parts by weight of the thermoplastic resin.
The flame-retardant resin composition according to any one of the above. Embedded image (In the above formula, R ^{3 to} R ¹⁰ 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. N is an integer of 0 or more. 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. ) 5. The composition according to claim 1, wherein (F) 0.01 to 2 parts by weight of a radical generator represented by the following general formula (4) is further added to 100 parts by weight of the thermoplastic resin. ~ 4
The flame-retardant resin composition according to any one of the above. Embedded image (X is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a carboxyl group, a hydroxyl group, an amino group,
It represents a nitrile group, a nitro group, or an epoxy group. N is an integer of 1 to 5. ) 6. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polystyrene resin. 7. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyester. 8. The flame-retardant resin composition according to claim 1, wherein (A) the thermoplastic resin is polybutylene terephthalate. 9. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyamide. 10. A molded article comprising the flame-retardant resin composition according to claim 1. 11. The molded article according to claim 10, which is a housing of an electric / electronic part, an automobile part, a mechanical mechanism part, an OA device, or a home appliance, and a part thereof.