JP2000191877A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fire retardant composition showing excellence in a permanent anti-static property, mechanical properties such as impact resistance, heat resistance, formability and heat stability by mixing a polystyrene-based resin, a polymer showing specific volume resistance, an organic phosphorous compound and a silicone-based compound, each mixing ratio being in a specific range. SOLUTION: A fire-retardant composition of the present invention is obtained by mixing 1-20 pts.wt. of an organic phosphorous compound represented by formula I and 0.01-5 pts.wt. of a silicone-based compound with 100 pts.wt. of a resin comprising 70-99 wt.% of a rubber-reinforced styrene-based resin and a polymer showing specific volume resistance of not more than 1012 Ωcm (wherein R1-R8 are each H or a 1-5C alkyl group, Ar1-Ar4 are each a phenyl group or a phenyl group substituted by an organic group containing no halogen; Y is a direct bond, O, S, SO2, C(CH3)2, CH2 or CHPh (Ph is phenyl): n is an integer not less than 0; k and m are each 0-2; and k+m is 0-2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a permanent antistatic property and excellent flame retardancy, impact resistance, rigidity, heat resistance, moldability and heat stability, The present invention relates to a thermoplastic resin composition which is excellent in flame retardancy and falling weight impact, and is suitable for a thin molded product.

[0002]

2. Description of the Related Art Plastic materials are excellent in properties such as mechanical properties such as impact resistance, moldability and appearance of molded articles, and are used in a wide range of fields such as home appliances, OA equipment, vehicles such as automobiles, and miscellaneous goods. Used in Materials for these applications can be further expanded in use if they are provided with antistatic properties and safety against flames, that is, flame retardancy, in addition to the properties of the materials. That is, copiers, printers, personal computers,
It can be used for fax machines, video game machines and their game software, electronic and electric equipment parts such as televisions, and various dustproof parts. Further, in these fields, the flame retardancy of chlorine- and bromine-free plastic materials has been strongly demanded year by year due to global environmental problems.

[0003] As a method for improving the antistatic property of a plastic material, a hydrophilic rubbery polymer obtained by copolymerizing a conjugated diene or / and an acrylic acid ester and a vinyl monomer having an alkylene oxide group is used. There is a method of graft polymerization of a vinyl monomer or a vinylidene monomer (JP-A-55-36237) and the like, and practical antistatic properties have been achieved.

A method for obtaining an antistatic resin by mixing a polyamide elastomer is disclosed in JP-A-62-116652. By mixing an ABS resin and a polyamide elastomer, a resin having a semi-permanent antistatic property can be obtained. It is disclosed that.

On the other hand, hitherto, as a method of making a thermoplastic resin flame-retardant without using a chlorine or bromine-based flame retardant, a method of blending an aromatic phosphate with a rubber-reinforced styrene resin (Japanese Patent Laid-Open No. 8-337703). And a method of blending a polyamide resin and ammonium polyphosphate with a rubber-reinforced styrene resin (JP-A-5-247342).

[0006]

However, Japanese Patent Application Laid-Open Nos. 55-36237 and 62-1166 describe above.
In the case of using the method of JP-A No. 52, there is a disadvantage that the flame retardancy is insufficient and the application is restricted.

Further, when the methods disclosed in JP-A-8-337703 and JP-A-5-247342 are used, no antistatic property is obtained.

The present invention provides a flame-retardant resin composition having excellent mechanical properties such as excellent permanent antistatic properties and impact resistance, heat resistance, moldability and heat stability, and containing no chlorine or bromine. The purpose is to provide things.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present invention has revealed that a phosphorus-based flame retardant has been added to a resin composition comprising a rubber-reinforced styrene resin and a polymer having a specific electric resistance value. It has been found that by blending in a specific amount, a thermoplastic resin composition having permanent antistatic properties and having remarkably excellent flame retardancy, mechanical properties, moldability, heat stability, and light resistance can be obtained. The invention has been reached.

That is, "(A) 70 to 99% by weight of a rubber-reinforced styrene resin and (B) a volume resistivity of 10 ¹² Ω.
(C) 1 to 30 parts by weight of an organic phosphorus compound represented by the general formula (1) per 100 parts by weight of the resin composition (A) comprising 1 to 30% by weight of a polymer having a molecular weight of 1 cm or less, and (D) silicone A flame-retardant thermoplastic resin composition comprising 0.01 to 5 parts by weight of a system compound. ".

[0011]

Embedded image (In the above formula, R ^{1 to} R ⁸ 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. )

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. In the present invention, weight means mass.

The rubber-reinforced styrenic resin (A) in the present invention has a structure in which a (co) polymer containing a styrene monomer is grafted to a rubbery polymer, and contains a styrene monomer. (Co) polymers include those having a structure in which a (co) polymer is not grafted to a rubbery polymer, and examples thereof include high impact polystyrene (HI-PS), ABS resin, AAS resin, AES resin, and MBS resin. .

More specifically, (a1) 5 to 80 parts by weight of a rubbery polymer and (a2) 95 to 20 parts by weight of a monomer or monomer mixture containing 20% by weight or more of an aromatic vinyl monomer. (A1) 5 to 100% by weight of a graft (co) polymer obtained by graft polymerization of
A (A2) vinyl-based (co) polymer obtained by polymerizing a monomer or a monomer mixture containing not less than 10% by weight is preferably from 0 to 95% by weight.

As the rubbery polymer (a1), those having a glass transition temperature of 0 ° C. or less are suitable, and diene rubbers are preferably used. Specifically, diene rubbers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, butyl acrylate-butadiene copolymer, and acrylics such as polybutyl acrylate Rubber, polyisoprene, ethylene-propylene-diene terpolymer and the like. 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 2 μm.
m, especially 0.20 to 1 μm, is preferable because of its excellent impact resistance. The average weight particle diameter of the rubber particles is “Rubbe”.
r Age Vol. 88p. 484-490 (196
0) by E.I. Schmidt, P .; H. Biddi
sodium ”described in“ Son ”(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) Measuring the diameter),
From a photograph of an ultra-thin section of resin taken with a transmission electron microscope,
It can be determined by a method of measuring the rubber particle diameter.

As the aromatic vinyl monomer, styrene,
Examples include α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, etc., with styrene being 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 (meth) acrylic monomer is used for the purpose of improving toughness and color tone. Acid ester monomers are preferably used. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable. Examples of the (meth) acrylate-based monomer include methyl and ethyl esters of acrylic acid and methacrylic acid with ethyl, propyl, n-butyl and i-butyl. Particularly, methyl methacrylate is preferred.

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

(A1) From the viewpoint of the impact resistance of the resin composition, the monomer or monomer mixture used in the graft (co) polymer may be at least 20% by weight of an aromatic vinyl monomer.
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 the monomer mixture is 95 to 20% by weight, more preferably 90-30% by weight
It is.

(A1) The ratio of the rubbery polymer to the monomer mixture in obtaining the graft (co) polymer is preferably at least 5 parts by weight of the rubbery polymer based on 100 parts by weight of the total graft copolymer. Is used in an amount of 10 parts by weight or more, 80 parts by weight or less, preferably 70 parts by weight or less. The amount of the monomer or monomer mixture is at most 95 parts by weight, preferably at most 90 parts by weight, at least 20 parts by weight, preferably at least 30 parts by weight. From the viewpoint of the impact resistance of the resin composition, the proportion of the rubbery polymer is preferably at least 5 parts by weight, and is preferably at most 80 parts by weight so as not to impair the impact resistance and the appearance of the molded article.

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 to a rubbery polymer. It is. (A) The graft ratio of the graft (co) polymer is not particularly limited, but is preferably from 20 to 200% by weight, particularly preferably from 25 to 100% by weight in order to obtain a resin composition having excellent impact resistance and gloss. . Here, the graft ratio is calculated by the following equation: graft ratio (%) = <amount of vinyl copolymer graft-polymerized 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 from 0.25 to 0.5.
A range of 80 dl / g, particularly 0.25 to 0.60 dl / g, is preferably used because a resin composition having excellent impact resistance can be obtained.

(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, if necessary, other vinyl monomers copolymerizable therewith can be used. For example,
The use of maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide to improve the heat resistance and flame retardancy of the resin composition can improve acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and phthalic acid. Acids, vinyl monomers containing a carboxyl group such as itaconic acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether,
Vinyl monomers containing an epoxy group such as p-glycidylstyrene, aminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-
Vinyl diethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, styrene having an amino group bonded to a benzene ring Vinyl monomers having an amino group or a substituted amino group, 2-hydroxyethyl acrylate,
2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentamethacrylate Hydroxyhexyl, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4 -Hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 1,
Vinyl monomers having a hydroxyl group such as 4-dihydroxy-2-butene, and oxazoline groups such as 2-propenyl-2-oxazoline, ethenyl-2-oxazoline, and 2- (1-butenyl) -2-oxazoline. By using a vinyl monomer containing a functional group such as a vinyl monomer, the mechanical properties, flame retardancy, and antistatic properties of the resin composition can be improved.

(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. It is 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-based monomer is mixed, from the viewpoint of toughness and impact resistance, 8
It is preferably 0% by weight or less, more preferably 75% by weight or less. When other vinyl monomers copolymerizable therewith are mixed, the content is preferably 60% by weight or less, more preferably 50% by weight or less.

(A2) The properties of the vinyl (co) polymer are not limited, but the intrinsic viscosity [η] (methyl ethyl ketone solvent, measured at 30 ° C.) is 0.40 to 0.80 dl / g, particularly 0.45 dl / g. ０．６0.60 dl / g, N, N-dimethylformamide solvent, when measured at 30 ° C., 0.35 to 0.85 dl / g, particularly 0.45 to
A resin composition having a range of 0.75 dl / g is preferable because 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 may be a conventional method such as bulk polymerization, suspension polymerization, emulsion polymerization, bulk-suspension polymerization, and solution-bulk polymerization. A method can be used.

The rubber-reinforced styrene resin (A) of the present invention has an intrinsic viscosity [η] (3
0 ° C) is 0.35 to 0.6 dl / g, preferably 0.4
０．５0.55 dl / g, and 0.40 to 0.80 in the case of N, N-dimethylformamide soluble matter.
dl / g, particularly preferably in the range of 0.5 to 0.7 dl / g, is preferred since an excellent flame-retardant resin composition is obtained.

In the present invention, (B) the volume resistivity value is 1
The polymer having a number average molecular weight of 100 to 10,000 is hereinafter referred to as a polymer exhibiting 0 ¹² Ωcm or less (hereinafter abbreviated as an antistatic polymer).
A polymer containing an alkylene oxide residue, a quaternary ammonium salt residue, a sulfonate residue, an ionomer residue, and the like, for example, (1) a number average molecular weight of 1,000 to 1
000 poly (alkylene oxide) glycol,
(2) polyetheramide, polyetherester, or polyetheresteramide containing an alkylene oxide residue having a number average molecular weight of 200 to 10,000,
(3) a vinyl polymer containing an alkylene oxide residue having a number average molecular weight of 100 to 10,000, (4) a vinyl polymer containing a quaternary ammonium salt residue, and (5) an alkali metal ionomer residue. Containing polymer, (6)
A vinyl polymer containing a residue of an alkali metal salt of sulfonic acid is exemplified.

Specifically, (1) poly (alkylene oxide) glycols include polyethylene glycol, polypropylene oxide glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, blocks of ethylene oxide and propylene oxide or random Copolymers and block or random copolymers of ethylene oxide and tetrahydrofuran are exemplified.

(2) Number average molecular weight 200 to 10,000
Examples of the polyether amide, polyether ester and polyether ester amide containing an alkylene oxide residue of (a1) include a polyamide-forming component or (a2) a polyester-forming component and (b) a number-average molecular weight of 20.
Block or graft copolymers obtained from reaction with diols containing 0 to 10,000 alkylene oxide residues.

(A1) As polyamide-forming components, salts of aminocarboxylic acids or lactams having 6 or more carbon atoms or diamines with diamines having 6 or more carbon atoms include ω-aminocaproic acid, ω-aminoenanthic acid,
Aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and aminocarboxylic acids such as 11-aminoundecanoic acid, 12-aminododecanoic acid or lactams such as caprolactam, enantholactam, caprylactam and laurolactam, and hexamethylenediamine −
Adipates, salts of diamine-dicarboxylic acids such as hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate, especially caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate are preferred. Used.

The (a2) polyester-forming components include terephthalic acid, isophthalic acid, and dicarboxylic acid.
Phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-
Dicarboxylic acid, diphenoxyethane dicarboxylic acid and 3
Aromatic dicarboxylic acids such as sodium sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2
Alicyclic dicarboxylic acids such as -cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-dicarboxymethylcyclohexyl, 1,4-dicarboxymethylcyclohexyl and dicyclohexyl-4,4'-dicarboxylic acid and succinic acid; Acids, oxalic acid, adipic acid, sebacic acid and aliphatic dicarboxylic acids such as decanedicarboxylic acid and aliphatic diol as ethylene glycol, 1,2- or 1,3-propylene glycol,
Examples thereof include 1,2-, 1,3-, 2,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and the like. Particularly, as the dicarboxylic acid, terephthalic acid, isophthalic acid, Ethylene glycol, 1,2- or 1,3-propylene glycol, and 1,4-butanediol as aliphatic diols with 1,4-cyclohexanedicarboxylic acid, sebacic acid, and decanedicarboxylic acid from the viewpoint of polymerizability, color tone and physical properties It is preferably used.

(B) Number average molecular weight 200 to 10,000
Examples of the diol containing an alkylene oxide residue include poly (ethylene oxide) glycol and poly (1,2-
Propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide)
Glycols include block or random copolymers of ethylene oxide and propylene oxide and block or random copolymers of ethylene oxide and tetrahydrofuran. Among these, poly (ethylene oxide) glycol is particularly preferably used because of its excellent antistatic properties.

Further, the number average molecular weight is from 200 to 10,000.
Examples of the diol containing an alkylene oxide residue include those added to both terminals such as hydroquinone, bisphenol A, and naphthalene.

(B) The diol having an alkylene oxide residue has a number average molecular weight of 100 to 10,000, preferably 400 to 6,000, in terms of polymerizability and antistatic properties.

The reaction between (a1) a polyamide-forming component or (a2) a polyester-forming component and (b) a diol containing an alkylene oxide residue is carried out by reacting (b) an ester depending on the terminal group of the diol containing the alkylene oxide residue. Reactions or amide reactions are possible.

A third component such as a dicarboxylic acid or a diamine can be used according to the above reaction.

In this case, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,
Aromatic dicarboxylic acid represented by 6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1,4-cyclohexane Alicyclic dicarboxylic acids represented by dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid and fats represented by succinic acid, oxalic acid, adipic acid, sebacic acid and decanedicarboxylic acid Group dicarboxylic acid, etc., especially terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and decanedicarboxylic acid are preferably used in view of polymerizability, color tone and physical properties of the resin composition. Trical such as trimellitic anhydride if necessary It is also possible to use phosphate anhydride.

Examples of the diamine component include aromatic, alicyclic and aliphatic diamines. Among them, the aliphatic diamine hexamethylenediamine is preferably used for economic reasons.

(2) The content of the diol containing an alkylene oxide residue is 30 to 90% by weight, preferably 40 to 80% by weight, based on the constituent units of polyetheramide, polyetherester and polyetheresteramide. .

(2) The degree of polymerization of polyetheramide, polyetherester, and polyetheresteramide is not particularly limited, but the relative viscosity measured at 25 ° C. in a 0.5% orthochlorophenol solution. (Ηr) is 1.1 to 4.0, preferably 1.5 to
The mechanical properties and the moldability of the final resin composition that provides a resin composition in the range of 2.5 are excellent and are preferable.

(3) Number average molecular weight 100 to 10,000
Examples of the vinyl polymer containing an alkylene oxide residue include polyethylene glycol (meth) acrylate,
Methoxypolyethylene glycol (meth) acrylate and the like, olefins such as ethylene, propylene and 1-butene, aromatic vinyl monomers such as styrene, hinyltoluene and α-methylstyrene, and maleimide monomers such as maleimide and N-phenylmaleimide And a copolymer with at least one vinyl monomer selected from vinyl cyanide monomers such as acrylonitrile, as described in the above (a1)
A graft copolymer obtained by polymerizing a rubbery polymer with a monomer containing at least one monomer selected from polyethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate is exemplified.

The proportion of the monomer containing an alkylene oxide residue is preferably in the range of 5 to 40% by weight in the vinyl polymer unit containing a poly (alkylene oxide) glycol residue.

(4) The vinyl polymer containing a quaternary ammonium salt residue includes a monomer containing a quaternary ammonium salt, an olefin monomer such as ethylene, propylene, 1-butene, and styrene. Hinyltoluene, α-
Aromatic vinyl monomers such as methylstyrene, (meth) acrylate monomers such as methyl (meth) acrylate and butyl (meth) acrylate, maleimide monomers such as maleimide and N-phenylmaleimide, Copolymers with at least one monomer selected from vinyl cyanide monomers such as acrylonitrile and the like are included. For example, "Leorex" SA-70 and AS-170 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. are commercially available.

The proportion of the monomer containing a quaternary ammonium salt is preferably in the range of 10 to 80% by weight in the vinyl polymer unit containing a quaternary ammonium salt residue.

(5) As the polymer containing an alkali metal ionomer residue, a copolymer of an olefinic monomer such as ethylene, propylene or 1-butene with (meth) acrylic acid may be lithium, sodium or potassium. And a resin ionized with at least one metal selected from the group consisting of:

A polymer containing an ionomer residue having a metal ion concentration of 1.5 mol / kg or more is preferred.

(6) Examples of the vinyl polymer containing a sulfonic acid alkali metal salt residue include monomers having a sulfonic acid alkali metal salt, such as potassium styrene sulfonate, sodium styrene sulfonate, and lithium styrene sulfonate. And ethylene, propylene, olefinic monomers such as 1-butene, styrene, hinyltoluene,
Aromatic vinyl monomers such as α-methylstyrene, (meth) acrylate monomers such as methyl (meth) acrylate and butyl (meth) acrylate, and maleimide monomers such as maleimide and N-phenylmaleimide Isomer, a copolymer with at least one vinyl monomer selected from vinyl cyanide monomers such as acrylonitrile, and the like. The content is preferably in the range of 10 to 80% by weight in the vinyl polymer unit containing an alkali metal salt residue.

(B) The volume resistivity of the antistatic polymer is 10 ¹² Ωcm or less, preferably 5 × 10 ¹¹ Ωcm or less, and the lower limit is not limited, but is 10 ⁵ Ωcm or more.
In particular, it is economically preferable to be 10 ⁶ Ωcm or more.

(B) If the volume resistivity of the antistatic polymer exceeds 10 ¹² Ωcm, the resulting final resin composition has insufficient antistatic properties, which is not preferable.

(B) The volume resistivity of the antistatic polymer is measured according to ASTM D257. When measuring from a resin composition, a molded product obtained by compression molding, injection molding, or the like of an antistatic polymer separated from the resin composition is measured. As a simple method, ASTM
According to D257, a line is drawn for the content of the conductor unit such as poly (alkylene oxide) glycol residue, quaternary ammonium salt residue, sulfonate residue and ionomer residue in the antistatic polymer and the volume resistivity value. The volume resistivity of the polymer can then be obtained by analyzing the content of the conductive units in any antistatic polymer.

In the present invention, (A) the resin composition is (A)
The rubber-reinforced styrene resin is blended in an amount of 70 to 99% by weight, preferably 80 to 95% by weight, and (B) 1 to 30% by weight, preferably 5 to 20% by weight of the antistatic polymer.

When the content of the rubber-reinforced styrenic resin (A) is less than 70% by weight, the resin composition becomes flexible and the rigidity is inferior. When the content exceeds 99% by weight, the antistatic property is insufficient, which is not preferable.

The (C) organophosphorus compound in the present invention includes:
It is a phosphoric ester represented by the following general formula (1).

[0059]

Embedded image (In the above formula, R ^{1 to} R ⁸ 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. Specifically, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol-bis (di-2,6
-Dimethylphenyl phosphate), resorcinol-
Bis (di-3,5-dimethylphenyl phosphate),
Resorcinol-bis (di-2,6-diethylphenylphosphate), resorcinol-bis (di-3,5-
Diethylphenyl phosphate), resorcinol-bis (di-2,6-dipropylphenyl phosphate),
Resorcinol bis (di-3,5-dipropylphenyl phosphate), hydroquinone-bis (di-2,6
-Dimethylphenyl phosphate), hydroquinone-
Bis (di-3,5-dimethylphenyl phosphate),
Hydroquinone-bis (di-2,6-diethylphenyl phosphate), resorcinol-bis (di-3,5-
Diethylphenyl phosphate), hydroquinone-bis (di-2,6-dipropylphenyl phosphate),
Hydroquinone-bis (di-3,5-dipropylphenyl phosphate), 4,4'-biphenylene-bis (di-2,6-dimethylphenyl phosphate), 4,4 '
-Biphenylene-bis (di-3,5-dimethylphenyl phosphate), 4,4'-biphenylene-bis (di-
2,6-diethylphenyl phosphate), 4,4'-
Biphenylene-bis (di-3,5-diethylphenyl phosphate), 4,4'-biphenylene-bis (di-
2,6-dipropylphenyl phosphate), 4,4 '
-Biphenylin-bis (di-3,5-dipropylphenylphosphate), resorcinol-bis (di-2-methylphenylphosphate), resorcinol-bis (di-3-methylphenylphosphate), resorcinol-bis (di-4) -Methylphenyl phosphate),
Resorcinol-bis (di-5-methylphenyl phosphate), resorcinol-bis (di-6-methylphenyl phosphate), hydroquinone-bis (di-2
-Methylphenyl phosphate), hydroquinone-bis (di-3-methylphenyl phosphate), hydroquinone-bis (di-4-methylphenyl phosphate), hydroquinone-bis (di-5-methylphenyl phosphate), hydroquinone-bis (di -6-methylphenyl phosphate), 4,4'-biphenylene-
Bis (di-2-methylphenyl phosphate), 4,4
'-Biphenylene-bis (di-3-methylphenyl phosphate), 4,4'-biphenylene-bis (di-4-
Methylphenyl phosphate), 4,4′-biphenylene-bis (di-5-methylphenyl phosphate),
4,4'-biphenylene-bis (di-5-methylphenyl phosphate), resorcinol-bis (diphenyl phosphate), hydroquinone-bis (diphenyl phosphate), 4,4'-biphenylene-bis (diphenyl phosphate), 4,4 '-Dihydroxydiphenyl-2,2-propane-bis (dixylenyl phosphate), 4,4'-dihydroxydiphenyl-2,2-propane-bis (dicresyl phosphate), 4,4'-
Dihydroxydiphenyl-2,2-propane-bis (diphenyl phosphate); and, in particular, resorcinol-bis (di-2,6-dimethylphenyl phosphate), hydroquinone-bis (di-2,6-dimethylphenyl phosphate), 4,4'-biphenylene-bis (di-2,6-dimethylphenyl phosphate), resorcinol-bis (di-4-methylphenyl phosphate), hydroquinone-bis (di-4-methylphenyl phosphate), resorcinol-bis (Diphenyl phosphate) has heat resistance, rigidity, surface gloss of molded products,
Excellent in flame retardancy and light resistance.

(B) The method for producing the organophosphorus compound is not particularly limited. For example, after reacting phosphorus oxychloride and hydroquinone in a solvent at a substantially 2: 1 molar ratio, 2,6-
Hydroquinone-bis (2,6-dimethylphenyl) phosphate can be obtained by adding an appropriate amount of dimethylphenol and reacting.

The silicone compound (D) used in the present invention may be any of silicone oil, silicone rubber and silicone resin.

Among the silicone compounds (D) used in the present invention, silicone rubber and silicone resin are chemical units selected from the units represented by the following general formulas (2) to (5) and mixtures thereof. Wherein R represents a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or allyl group, respectively. An organosiloxane resinous polymer or copolymer, and at room temperature of about 100 to 300,0
A resin having a viscosity of 000 centipoise is preferable, but is not limited to the above silicone rubber and silicone resin.

[0063]

Embedded image The silicone oil used in the present invention is represented by the following general formula (6) (where R represents an alkyl group or a phenyl group, and n is an integer of 1 or more). The silicone oil used is 0.65-10
A viscosity of 000 centistokes is preferred,
As long as it is the above silicone oil, it is not limited to it.

[0064]

Embedded image In addition, the silicone-based compound as described above further has an epoxy group, an acryloxy group, a methacryloxy group, a vinyl group, a phenyl group, an N-β- (N-vinylbenzylamino) as a reactive functional group in a molecule or at a molecular terminal. Those containing an ethyl-γ-aminoalkyl hydrochloride group and a hydroxyl group can be used, and among them, those containing an epoxy group, an acryloxy group and a methacryloxy group can be preferably used.

In particular, among silicone compounds, in the case of silicone rubber, a powdery one at room temperature is preferred, and in the case of a silicone resin, a powdery or flake-like one is preferred.

As the silicone compound used in the present invention, silicone oil, silicone rubber and silicone resin can be used, but they are flame-retardant, heat-resistant, bleed-out-resistant, contact-pollution-resistant, and after heat-moisture treatment. Silicone rubber and silicone resin are preferred from the viewpoint of bleed-out resistance.

As the silicone compound (D) used in the present invention, a compound further containing a silica filler can be used. In particular, when a silica filler is added to the silicone rubber, the silicone rubber in the resin composition can be used. This is preferred because the dispersibility of the resin is improved, and the flame retardancy and heat resistance are improved. In particular, it is more effective in the case of silicone rubber powder.

As a method for mixing the silicone rubber and the silica filler, a generally known method can be applied. Further, it is preferable to mix an alkoxysilane coupling agent with the composition comprising the silicone rubber and the silica filler.

Such silane coupling agents include at least one alkoxy group having 1 to 4 carbon atoms in the molecule, and further include an epoxy group, an acryloxy group, a methacryloxy group, a vinyl group, a phenyl group, an N-β- A silane coupling agent containing (N-vinylbenzylamino) ethyl-γ-aminoalkyl hydrochloride group and hydroxyl group can be used. Among them, a silane coupling agent containing epoxy group, acryloxy group and methacryloxy group can be used. An agent can be preferably used.

Among the (D) silicone compounds used in the present invention, a thermogravimetric differential thermogravimeter (Tg / DTA-200, manufactured by Seiko Denshi Kogyo KK) can be used at room temperature (30 g). ℃) ~ 900 ℃ temperature range 40 ℃
In a heating test carried out at a temperature rising rate of 800 ° C./min, the weight loss at 800 ° C. compared to room temperature is 70% or less, preferably 5%.
Those having 0% by weight or less, more preferably 30% by weight or less are particularly preferable because the flame retardancy of the resin composition is remarkably improved.

Of the silicone compounds (D) used in the present invention, silicone oil silicone rubber and silicone resin can be used alone or as a mixture of one or more.

The silicone compound (D) is as follows:
Usually, those manufactured by a known method can be used.

In order to further exert the effect of the present invention, (A)
(C) Organophosphorus compound 1 per 100 parts by weight of resin composition
To 20 parts by weight, preferably 5 to 20 parts by weight, and 0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight of the silicone compound (D).
It is important to add ~ 2 parts by weight.

If the amounts of the components (C) and (D) are out of the ranges, at least one of the properties of drip-extinguishing, heat resistance, impact resistance, and falling weight impact of a thin molded product is undesirably deteriorated.

In the present invention, a higher fatty acid amide may be added for the purpose of further enhancing the drip-extinguishing property and the falling weight impact of a thin molded product.

The higher fatty acid amide includes, for example, stearic acid monoamide, stearic acid bisamide, lauric acid bisamide, lauric acid ethylene bisamide, stearic acid ethylene bisamide, hydroxystearic acid bisamide, hydroxystearic acid ethylene bisamide, and particularly stearic acid. Ethylene bisamide, hydroxystearic acid ethylene bisamide, and lauric acid ethylene bisamide have excellent flame retardancy and impact resistance, and can be suitably used.

The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include (A) a rubber-reinforced styrene resin, (B) an antistatic polymer, (C) an organic phosphorus compound,
(D) It is prepared by premixing a silicone resin or not and supplying it to an extruder or the like, and sufficiently kneading the mixture in a temperature range of 150 ° C to 300 ° C. In this case, the product is produced by melt-kneading with a kneader such as a single-screw extruder, a twin-screw extruder, a tri-screw extruder, a roll, or a kneader equipped with a screw such as “Dalmage” or “Full-flight” type. The resin composition (a) of the present invention can be blended with this and another thermoplastic resin. For example, polyphenylene ether, polycarbonate, polyglutarimide, polycyclohexane dimethylene terephthalate and the like to improve impact resistance, heat resistance, polyolefin, polybutylene terephthalate,
By mixing polyethylene terephthalate or the like, chemical resistance can be improved. Further, if necessary, antioxidants such as metal salts of sulfonic acid and anionic, cationic and nonionic surfactants, and antioxidants such as hindered phenolic, phosphorus and sulfur antioxidants and Heat stabilizers, UV absorbers (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (eg, montanic acid and its salts, esters, half esters, stearyl alcohol, and ethylene wax). Can be blended.

The thermoplastic resin composition of the present invention is melt molded and used as a resin molded product. This resin molded product is characterized by excellent drip-extinguishing properties at a molded product thickness of 0.5 to 3 mm, especially 2 mm or less, exhibiting V-2 flame retardancy according to UL94 standard, and having excellent falling weight impact of thin molded products. , Printers, personal computers, displays, CRT displays, faxes,
It is useful for members of DVD drives, PD drives, floppy disk drives, storage devices such as DVD drives, PD drives, and floppy disk drives, as well as copy, word processors, and notebook computers.

[0079]

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 (A) Preparation of Rubber-Reinforced Styrenic Resin A method for preparing a rubber-reinforced styrene-based resin 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. This solution is cooled to 8000 rpm (480 × 10 ³ s ⁻¹ ).
(Acceleration 10,000G (about 100 × 10 ³ m / s ² ))
After centrifugation for 30 minutes, insoluble matter was filtered. This insoluble content is 7
It dried under reduced pressure at 0 degreeC for 5 hours, and measured the weight (n).

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

(A1) Preparation of Graft Copolymer Polybutadiene latex (average rubber particle diameter 0.3 μm)
In the presence of 60 parts (in terms of solid content), 40 parts of a monomer mixture composed of 73% of styrene and 27% of acrylonitrile were added to carry out emulsion polymerization. The obtained graft copolymer is coagulated with sulfuric acid, neutralized with caustic soda, washed,
After filtration and drying, a powdery graft copolymer was prepared. The obtained graft copolymer had a graft ratio of 39%. This graft copolymer has a styrene structural unit of 7
It contained 15.8% of a non-grafting copolymer consisting of 3% and 27% of acrylonitrile. The intrinsic viscosity of the soluble portion of methyl ethyl ketone is 0.30 dl /
g.

(A2) Preparation of Vinyl Copolymer A vinyl copolymer was prepared by subjecting a monomer mixture composed of 72% of styrene and 28% of acrylonitrile to suspension polymerization.
The intrinsic viscosity of the obtained vinyl copolymer in a methyl ethyl ketone solvent was 0.50.

Reference Example 2 (B) Preparation of Antistatic Polymer <B-1> Caprolactam 40 parts, number average molecular weight 200
56.3 parts of polyethylene glycol and 4.8 parts of terephthalic acid as antioxidants (Irganox 1098)
0.2 parts by weight and 0.1 part by weight of antimony trioxide were charged into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated and stirred at 260 ° C. for 50 minutes while flowing a small amount of nitrogen to obtain a transparent homogeneous solution. After that, 260 ° C, 0.5m
Polymerization was performed for 3 hours under the condition of mHg or less to obtain a transparent polymer. The polymer was discharged in a gut shape on a cooling belt and pelletized to prepare pellet-like polyetheresteramide <B-1>.

The obtained polyetheresteramide was placed in a 0.5% orthochlorophenol solution at 25 ° C.
Is 2.01 and the volume resistivity is 1 × 10 ⁹ Ωcm.

<B-2> 90 parts of caprolactam, 9.4 parts of polyethylene glycol having a number average molecular weight of 2,000, and 0.8 parts of terephthalic acid are mixed with 0.2 parts by weight of an antioxidant (Irganox 1098) and 0 parts of antimony trioxide. .05
After being charged together with the weight parts into a reaction vessel equipped with a helical ribbon stirring blade, a polyetheresteramide <B-2> was prepared according to Reference Example <B-1>.

The obtained polyetheresteramide was placed in a 0.5% orthochlorophenol solution at 25 ° C.
Is 2.11 and the volume resistivity is 3 × 10 ¹³ Ωcm.

<B-3> Caprolactam was polymerized under pressure to prepare a polyamide <B-3>.

The obtained polyamide has a relative viscosity (ηr) of 2.10 and a volume resistivity value of 5 × 10 ¹⁴ measured at 25 ° C. in a 0.5% orthochlorophenol solution.
Ωcm.

Reference Example 3 (C) Organophosphorus Compound <C-1> Resorcinol-bis (di-2,6-dimethylphenyl) phosphate "PX-200" (manufactured by Daihachi Chemical Co., Ltd.) was used. .

<C-2> Resorcinol-bis (diphenyl phosphate) “CR-733S” (manufactured by Daihachi Chemical Co., Ltd.) was used.

Reference Example 4 (D) Silicone Compound <D-1>"DY33-7" which is a fine silicone rubber powder
23 "(manufactured by Dow Corning Toray Silicone Co., Ltd.)
used. This silicone rubber is a thermogravimetric / differential thermometer (TG / DTA-20, manufactured by Seiko Instruments Inc.)
0), the temperature range of 30 ° C. to 900 ° C. in air is set to 40 ° C.
As a result of performing a heating test at a heating rate of / min, the weight loss at 800 ° C. was 55% by weight.

<D-2>"DC4-7105" (manufactured by Dow Corning Toray Silicone Co., Ltd.), which is a fine silicone resin powder, was used. This silicone resin was subjected to a heating test in the same manner as described above. As a result, the weight loss at 800 ° C. was 26% by weight.

Examples 1 to 8, Comparative Examples 1 to 8 (A) Rubber-reinforced styrene resin prepared in Reference Examples,
(B) antistatic polymer, (C) organophosphorus compound, (D)
The silicone-based compound was mixed at the compounding ratio shown in Table 1, melt-kneaded and extruded with a vented 30 mmφ twin screw extruder to produce a pellet-shaped polymer. Next, the test piece was molded by an injection molding machine, and the physical properties were measured under the following conditions.

(1) 1/2 "Izod impact strength: AS
TM D256-56A (2) Drop weight impact strength: Disc molded product (40φ × 2mmt)
A weight with a 5R tip is dropped on the
The height at which 0% fracture occurs and the weight of the weight at that time are determined.

(3) MFR: JIS K7210 [20
0 ° C., load: 5 kgf (49.03 N)] The higher the numerical value, the better the fluidity during molding.

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

(5) Surface specific resistance value: 2 mmt × 40 m
The measurement was carried out under the following conditions using a disk of mφ. For the measurement, a super insulation resistance meter SM-10 manufactured by Toa Denpa Kogyo KK was used.

(1) Immediately after molding, the surface was washed with an aqueous solution of a detergent “Mamaroyal” (manufactured by Lion Corporation), and then sufficiently washed with distilled water to remove water on the surface.
The measurement was performed in a 50% RH atmosphere.

(2) After molding, 10% in 23 ° C. and 50% RH.
After leaving it for 0 days, it was washed with an aqueous solution of a detergent "Mamaroyal" (manufactured by Lion Corporation), and then sufficiently washed with distilled water to remove water from the surface.
It was measured in a 0% RH atmosphere.

(6) Flame retardancy: A vertical flame retardant test was performed at 1/8 "× 1 / according to the evaluation standard defined in the UL94 standard.
The test was performed on 2 ″ × 5 ″ and 1/16 ″ × 1/2 ″ × 5 ″ combustion test specimens. The flame retardancy level was V-0>V-1>V-2> H
It decreases in the order of B.

Note that the burning time is a value obtained by summing the times until the flames out in the five burning tests.

Tables 2 and 3 show the measurement results.

[0104]

[Table 1]

[0105]

[Table 2] ●

[Table 3]

From the results in Tables 2 and 3, the following is clear. All of the resin compositions of the present invention (Examples 1 to 8) have remarkably improved flame retardancy, and are excellent in impact resistance, fluidity, heat resistance, and particularly, falling weight impact resistance in a thin wall. It has a lower surface resistivity. In addition, the surface specific resistance value does not change even when the surface of the molded article is washed or changed with time, and exhibits excellent permanent antistatic properties.

That is, the resin composition of the present invention has excellent flame retardancy, mechanical properties, fluidity, heat resistance and permanent antistatic properties.

On the other hand, when the compounding amount of the antistatic polymer (B) is less than 1% by weight (Comparative Example 1), the antistatic property is poor,
When the amount of the antistatic polymer (B) exceeds 40% by weight (Comparative Example 2), the flame retardancy and heat resistance are poor.

When the amount of the phosphorus-based flame retardant (C) is less than 1 part by weight (Comparative Example 3), the flame retardancy is poor, and when the amount of the flame retardant (C) is more than 20 parts by weight (Comparative Example 3). Example 4) is inferior in impact resistance and heat resistance.

(D) The compounding amount of the silicone compound is 0.1%.
When the amount is less than 01 parts by weight (Comparative Example 5), the flame retardancy is poor.
When the amount exceeds the weight part (Comparative Example 6), the impact resistance and the flame retardancy are inferior.

When the volume resistivity of the antistatic polymer (B) exceeds 10 ¹² Ωcm (Comparative Examples 7 and 8), the impact resistance, fluidity and antistatic properties are poor.

[0112]

The resin composition of the present invention exhibits excellent heat resistance, fluidity, flame retardancy and permanent antistatic properties without impairing the mechanical properties of the thermoplastic resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) // (C08L 51/04 55:02 101: 12 83:04) F term (Reference) 4F071 AA12X AA22X AA34X AA47 AA54 AA57 AA67 AA77 AC15A AE07A AF37A AF37Y AF47A AF47Y AH12 BA01 BB05 4J002 BC06W BN04W BN14W BN15W BN15X BN16W CF10X CH02X CL07X CL08X CP033 CQ014 EW046 FD010 FD030 FD050FD

Claims (6)

[Claims] 1. A rubber-reinforced styrene resin (A) 70 to 99.
(B) a resin composition 10 comprising 1 to 30% by weight of a polymer having a volume resistivity of 10 ¹² Ωcm or less.
(C) 1 to 20 parts by weight of the organic phosphorus compound represented by the general formula (1), and (D) silicone compound 0 to 0 parts by weight.
A flame-retardant thermoplastic resin composition characterized in that it contains from 0.01 to 5 parts by weight. Embedded image (In the above formula, R ^{1 to} R ⁸ 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. ) 2. A silicone wherein the weight loss of the silicone compound (D) in air is 70% by weight or less in a heating test (heating rate: 40 ° C./min) at room temperature (30 ° C.) at 800 ° C. The flame-retardant resin composition according to claim 1, which is a rubber and / or a silicone resin. 3. The polymer (B) has an average number molecular weight of 100 to 1
2. A polymer containing a residue selected from 000 alkylene oxide residues, quaternary ammonium salt residues, and alkali metal ionomer residues.
Or the flame-retardant resin composition according to 2. 4. The flame-retardant resin composition according to claim 1, wherein the polymer (B) is polyetheramide, polyetherester or polyetheresteramide. 5. The thermoplastic resin composition according to claim 1, wherein the flame retardancy based on UL94 standard is V-2 when the test piece has a thickness of 0.5 to 3.5 mm.
4. The flame-retardant thermoplastic resin composition according to any one of 4. 6. An injection-molded article comprising the flame-retardant thermoplastic resin composition according to claim 1.