JPH11166099A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition capable of manifesting permanent antistatic properties and flame retardance by compounding a resin composition comprising a rubber-reinforced styrene-based resin and a polymer having a specific electrical resistance value with a specified amount of a radical former having a specific structure. SOLUTION: This composition is obtained by compounding (A) 100 pts.wt. resin composition comprising (i) 60-99 wt.% rubber-reinforced styrene-based resin and (ii) 1-40 wt.% polymer having <=10<13> Ωcm volume resistivity value with (B) 0.01-5 pts.wt. radical former. The component (ii) is preferably a polymer containing a poly(alkylene oxide)glycol residue, a quaternary ammonium salt residue or the like. The component (B) preferably has any one of chemical bonds such as an O-O bond or a C-C bond in the molecule and further >=200 deg.C half-life of 1 min. Furthermore, a phosphorus-based flame retardant in an amount of 0.1-30 pts.wt. based on 100 pts.wt. component (A) is preferably compounded in the component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition having permanent antistatic properties and having excellent flame retardancy, impact resistance, rigidity, heat resistance and moldability.

[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 is possible to develop applications for housings of electronic machines and electric appliances such as fax machines, video game machines and their game software, televisions, and their parts, 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 point that the flame retardancy is not sufficient and the use is restricted. Also, JP-A-8-3
In the case of using the method of Japanese Patent Application Laid-Open No. 37703 or Japanese Patent Application Laid-Open No. 5-247342, no antistatic property is obtained.

The present invention provides a flame-retardant resin composition which has excellent mechanical properties such as excellent antistatic properties and impact resistance, heat resistance, and moldability, and does not contain chlorine and bromine. The purpose is to:

[0008]

Means for Solving the Problems According to the present invention, as a result of intensive studies to solve the above problems, a resin composition comprising a rubber-reinforced styrene resin and a polymer having a specific electric resistance value has a specific chemical structure. It has been found that by blending a specific amount of a radical generator having the same, a thermoplastic resin composition having permanent antistatic properties and having remarkably excellent flame retardancy, mechanical properties, heat resistance, and moldability can be obtained. The present invention has been reached.

That is, "(A) 60 to 99% by weight of a rubber-reinforced styrene resin and (B) a volume resistivity of 10 ¹³ Ω.
(C) 0.01 to 5 parts by weight of a radical generator with respect to 100 parts by weight of (a) a resin composition comprising 1 to 40% by weight of a polymer having a molecular weight of 1 cm or less. Flammable thermoplastic resin composition. ".

[0010]

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) of the present invention has a structure in which a (co) polymer containing a styrene monomer is grafted to a rubbery polymer, and a resin containing a styrene monomer. (Poly) includes those having a structure in which a (co) polymer is not grafted to a rubbery polymer. Examples thereof include high impact polystyrene (HI-PS), acrylonitrile-butadiene-styrene copolymer (ABS resin), and acrylonitrile- Acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), methyl methacrylate-butadiene-styrene copolymer (MB
S resin).

Specifically, (a1) rubbery polymer 5-80
(A1) Graft (co) polymer 5 obtained by graft polymerization of 95 to 20 parts by weight of a monomer or monomer mixture containing 20% by weight or more of (a2) an aromatic vinyl monomer in parts by weight (A2) a vinyl (co) polymer obtained by polymerizing a monomer or a monomer mixture containing (a3) an aromatic vinyl monomer in an amount of 20% by weight or more and (A3) an aromatic vinyl monomer,
Those comprising 5% by weight are preferred.

As the rubbery polymer (a1), 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, diene rubber such as butyl acrylate-butadiene copolymer, acrylic rubber such as polybutyl acrylate, polyisoprene, An ethylene-propylene-diene-based terpolymer is exemplified. Among them, polybutadiene or butadiene copolymer is preferred.

Although the rubber particle diameter of the rubbery polymer is not particularly limited, the weight average particle diameter of the rubber particles is 0.15 to 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) (Determining the diameter).

(A2) Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, etc., with styrene being particularly preferred.

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

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

The monomer or monomer mixture used in the (A1) graft (co) polymer contains (a2) at least 20% by weight of an aromatic vinyl monomer from the viewpoint of the impact resistance of the resin composition. Preferably, it is more preferably at least 50% by weight. When a vinyl cyanide monomer is mixed, the amount is preferably 60% by weight or less, and more preferably 50% by weight or less, from the viewpoint of moldability of the resin composition. When a (meth) acrylate monomer is mixed, toughness,
From the viewpoint of impact resistance, the content is preferably 80% by weight or less, and more preferably 75% by weight or less. 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 proportion of the rubbery polymer is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and 80 parts by weight or less, preferably 70 parts by weight in order not to impair the impact resistance and appearance of the molded article. The following are 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. (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 on rubbery polymer> / <rubber content of graft copolymer> × 100

The properties of the non-grafted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component is 0.25-0.
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.

The (A2) vinyl (co) polymer is a copolymer containing (a3) an aromatic vinyl monomer as an essential component. (A3) Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, o-ethylstyrene, etc., with styrene being particularly preferred. One or more of these can be used.

(A3) 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. 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.

Further, if necessary, other vinyl monomers copolymerizable therewith can be used. For example,
Maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide are used to improve the heat resistance and flame retardancy of the resin composition by using acrylic acid, methacrylic acid,
Carboxyl-containing vinyl monomers such as maleic acid, maleic anhydride, phthalic acid and itaconic acid, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl Ether, p-
Vinyl monomers containing an epoxy group such as glycidylstyrene, aminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine , Methallylamine, N-methylallylamine, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, vinyl having an amino group or a substituted amino group such as styrene having an amino group bonded to a benzene ring Monomer, 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 functional group-containing vinyl monomer such as a vinyl monomer, the mechanical properties, flame retardancy and antistatic properties of the resin composition can be improved.

From the viewpoint of the impact resistance of the resin composition, the proportion of the aromatic vinyl monomer (a3), which is a constituent component of the (A2) vinyl (co) polymer, is 20% by weight based on all monomers. % Or more, more preferably 50% by weight or more. When mixing a vinyl cyanide monomer,
From the viewpoint of impact resistance and fluidity, it is preferably at most 60% by weight, more preferably at most 50% by weight. When mixing (meth) acrylate monomers,
From the viewpoint of toughness and impact resistance, 80% by weight or less is preferable,
Further, 75% by weight or less is preferably used. 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-based (co) polymer are not limited, but the intrinsic viscosity [η] (methyl ethyl ketone solvent, measured at 30 ° C.) is 0.40 to 0.65 dl / g, particularly 0.45 dl / g. In the range of 0.55 dl / g to 0.35 to 0.85 dl / g, especially 0.45 to
A resin composition in the range of 0.70 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.

In the present invention, (B) the volume resistivity value is 1
The polymer exhibiting 0 ¹³ Ωcm or less (hereinafter abbreviated as antistatic polymer) contains poly (alkylene oxide) glycol residue, quaternary ammonium salt residue, sulfonate residue, ionomer residue and the like. Examples of the polymer include (1) poly (alkylene oxide) glycol, (2) polyetheramide, polyetherester, or polyetheresteramide containing a poly (alkylene oxide) glycol residue, and (3) poly (alkylene oxide). (Alkylene oxide) vinyl polymer containing a glycol residue, (4) vinyl polymer containing a quaternary ammonium salt residue, (5) polymer containing an alkali metal ionomer residue, (6) sulfonic acid And vinyl polymers containing an alkali metal salt residue.

Specifically, (1) the poly (alkylene oxide) glycol has a number average molecular weight of 1,000 to
5,000,000 poly (alkylene oxide) glycols, polyethylene glycol, polypropylene oxide glycol, poly (tetramethylene oxide)
Glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran.

(2) The polyether amide, polyether ester or polyether ester amide containing a poly (alkylene oxide) glycol residue includes (a1) a polyamide-forming component or (a2) a polyester-forming component and (b) Block or graft copolymer obtained from reaction with poly (alkylene oxide) glycol.

(A1) As a polyamide-forming component, a salt of an aminocarboxylic acid having 6 or more carbon atoms or a lactam or a diamine having 6 or more carbon atoms with a dicarboxylic acid includes ω-aminocaproic acid, ω-aminoenanthic acid,
Aminocarboxylic acids such as ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid, or lactams and hexamethylene such as caprolactam, enantholactam, caprylactam and laurolactam. Salts of diamine-dicarboxylic acids such as diamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate, especially caprolactam, 12-aminododecanoic acid, and hexamethylenediamine-adipate Is preferably used.

(A2) As the polyester-forming component, terephthalic acid, isophthalic 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) The poly (alkylene oxide) glycol includes poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, Examples include poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Among these, poly (ethylene oxide) glycol is particularly preferably used because of its excellent antistatic properties.

The poly (alkylene oxide) glycol also includes those added to both terminals, such as hydroquinone, bisphenol A, and naphthalene.

(B) The number average molecular weight of the poly (alkylene oxide) glycol is preferably in the range of 200 to 6000 from the viewpoint of polymerizability and antistatic properties.

(A1) a polyamide-forming component or (a)
2) The reaction between the polyester-forming component and (b) poly (alkylene oxide) glycol may be an ester reaction or an amide reaction depending on the terminal group of (b) poly (alkylene oxide) glycol.

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 poly (alkylene oxide) glycol residue is preferably from 30 to 90% by weight, more preferably from 40 to 90% by weight in the structural unit of polyetheramide, polyetherester or polyetheresteramide.
~ 80% by weight.

Also, (2) poly (alkylene oxide)
The degree of polymerization of the polyetheramide, polyetherester, or polyetheresteramide containing a glycol residue is not particularly limited, but the relative viscosity (ηr) measured at 25 ° C. in a 0.5% orthochlorophenol solution. ) Is preferably in the range of 1.1 to 4.0, particularly 1.5 to 2.5, because the final resin composition has excellent mechanical properties and moldability.

(3) Examples of the vinyl polymer containing a poly (alkylene oxide) glycol residue include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and ethylene.
Olefins such as propylene, 1-butene, styrene,
At least one vinyl monomer selected from aromatic vinyl monomers such as hinyltoluene and α-methylstyrene, maleimide monomers such as maleimide and N-phenylmaleimide, and vinyl cyanide monomers such as acrylonitrile. And a monomer containing at least one monomer selected from polyethylene glycol (meth) acrylate and methoxypolyethylene glycol (meth) acrylate on the above-mentioned (a1) rubbery polymer. And the like.

The proportion of the monomer containing a poly (alkylene oxide) glycol group is poly (alkylene oxide)
5 to 4 of vinyl polymer units containing a glycol residue
A range of 0% by weight is preferred.

(4) Examples of the vinyl polymer containing a quaternary ammonium salt residue include a monomer containing a quaternary ammonium salt group, 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 base 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 olefin monomer such as ethylene, propylene or 1-butene and (meth) acrylic acid may be prepared by using lithium, sodium and potassium. And a resin ionized with at least one metal selected from the group consisting of: Among them, a polymer containing an ionomer residue having a metal ion concentration of 1.5 mol / kg or more is preferable.

(6) Examples of the vinyl polymer containing a sulfonic acid alkali metal salt residue include monomers having a sulfonic acid alkali metal base, 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 And a copolymer with at least one vinyl monomer selected from vinyl cyanide monomers such as acrylonitrile.

The proportion of the monomer having a sulfonic acid alkali metal base is preferably in the range of 10 to 80% by weight based on the vinyl polymer unit containing the sulfonic acid alkali metal salt residue.

(B) The volume resistivity of the antistatic polymer is 10 ¹³ Ωcm or less, preferably 10 ¹² Ωcm or less. The lower limit is not particularly limited, but is 10 ⁵ Ωcm or more.
In particular, a value of 10 ⁶ Ωcm or more is economical and preferable. (B) When the volume resistivity of the antistatic polymer exceeds 10 ¹³ Ωcm, the antistatic properties of the final resin composition obtained are insufficient, and the object of the present invention cannot be achieved.

(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 60 to 99% by weight, preferably 70 to 95% by weight, and (B) 1 to 40% by weight, preferably 5 to 30% by weight of the antistatic polymer.

When the content of the rubber-reinforced styrene resin (A) is less than 60% by weight, the resin composition becomes flexible and the rigidity is poor. When it exceeds 99% by weight, the antistatic property is insufficient.

The radical generator (C) in the present invention is not particularly limited as long as it is a compound capable of generating a radical by light or heat.
A compound having any one type of —C— bond can be used. Among such radical generators, those that do not generate radicals during melting compound but generate radicals during combustion are preferable in order to obtain a high effect as a flame retardant. For this purpose, the radical generator used in the present invention has a one-minute half-life of 20 minutes.
It is preferably at least 0 ° C., more preferably 25 ° C.
0 ° C or higher.

Here, the one-minute half-life can be measured by a known method. 0.1 mol of radical generator
% Benzene solution, sealed in a glass ampoule purged with nitrogen, attached to 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, the relationship of X = 2 / a is substituted into the above equation to obtain 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.

Preferred (C) radical generators include
Specific examples include a compound represented by the following general formula (1).

[0060]

Embedded image Here, in the above formula, R ^{1 to} R ⁶ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.

The monovalent organic residue having 1 to 10 carbon atoms specifically includes 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. Groups, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, allyl group, phenyl group, xylyl group, cumenyl group, naphthyl group, etc., and methyl group, ethyl group, and phenyl group are preferable. Particularly, a methyl group and a phenyl group are preferable.

Among the radical generators represented by the general formula (1), those represented by the following general formula (2) can be more preferably used in terms of flame retardancy.

[0063]

Embedded image Here, in the above formula, R ^{2 to} R ⁵ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.

Here, specific examples of the monovalent organic residue having 1 to 10 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. Groups, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, allyl group, phenyl group, xylyl group, cumenyl group, naphthyl group, etc., and methyl group, ethyl group, and phenyl group are preferable. Particularly, a methyl group and a phenyl group are preferable.

Further, as the radical generator represented by the above general formula (2), those represented by the following general formula (3) are particularly preferable in view of flame retardancy.

[0066]

Embedded image

In the present invention, a radical generator having a —O—O— bond in the molecule can also be preferably used.

Specific examples of the radical generator having a —O—O— bond in a molecule include a compound represented by the following general formula (4).

[0069]

Embedded image In the above formula, R ^{7 to} R ⁹ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms, and these organic residues may be further substituted with an —OOH group. .

Here, specific examples of the monovalent organic residue having 1 to 10 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. Group, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, cyclohexyl group, allyl group, phenyl group, xylyl group, cumenyl group, naphthyl group, and substituted products thereof.

Among them, in particular, one or a mixture of two or more selected from the following formula (5) can be preferably used from the viewpoint of flame retardancy.

[0072]

Embedded image

In order to exert the effect of the present invention, the amount of the radical generator (C) is 0.01 to 5 parts by weight, preferably 0.02 to 2 parts by weight, per 100 parts by weight of the resin composition (A).
Parts by weight, more preferably 0.05 to 1 part by weight.
When the amount of the radical generator (C) is within the above range, drip is accelerated during combustion, and high flame retardancy is obtained.

Further, by further adding (D) a phosphorus-based flame retardant to the resin composition (A) of the present invention, more excellent flame retardancy can be obtained.

The (D) phosphorus-based flame retardant in the present invention is not particularly limited as long as it is an organic or inorganic compound containing phosphorus. For example, red phosphorus, ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate,
Phosphine oxide and the like. Among them, ammonium polyphosphate and phosphate are preferable, and the following formula (6)
The aromatic phosphate represented by the following formula (1) can be more preferably used.

[0076]

Embedded image (However, the above formulas R ^{10 to} R ¹⁷ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Ar
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, SO
₂ , C (CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. Also, k,
m is an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. )

First, the structure of the flame retardant represented by the formula (6) will be described. In the formula (6), 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,
Preferably, k and m are each an integer of 0 or more and 1 or less, and particularly preferably, k and m are each 1.

In the formula (6), R ^{10 to} R ¹⁷ 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.

In the present invention, when (D) a phosphorus-based flame retardant is blended, 0.1 parts by weight of (a) the resin composition is used.
It is 1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight. (D) When the compounding amount of the phosphorus-based flame retardant is within the above range, the flame retardancy is further improved.

The flame-retardant resin composition of the present invention is usually produced by a known method. For example, (A) a rubber-reinforced styrene resin, (B) an antistatic polymer, (C) a radical generator,
(D) A phosphorus-based flame retardant and other necessary additives are supplied to an extruder or the like with or without pre-mixing,
It is prepared by sufficiently melting and kneading in a temperature range of 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, and a kneader equipped with a “unimelt” type screw.

The resin composition (A) of the present invention may be made of other thermoplastic polymers compatible with the resin composition of the present invention, for example, polyamide, polybutylene terephthalate, polyethylene terephthalate, polycyclohexane dimethylene terephthalate, polycarbonate, Polyphenylene ether,
The performance as a molding resin can be improved by mixing polyglutarimide and the like.

The resin composition (A) of the present invention may further comprise, if necessary, a metal salt of sulfonic acid, an antistatic agent such as an anionic, cationic or nonionic surfactant, a hindered phenol or phosphorus compound. -Based, antioxidants such as sulfur-based antioxidants, heat stabilizers, ultraviolet absorbers (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and release agents (montanic acid and its salts, esters, half thereof) Ester, stearyl alcohol, stella amide, ethylene bis stearyl amide, ethylene wax, etc.), flame retardant aids such as fluororesins and phenolic resins, and fillers such as glass fibers, carbon fibers, and metal fibers. it can.

The thermoplastic resin composition of the present invention is melt-molded and used as various resin molded products. This resin molded product is excellent in drip-extinguishing property at a molded product thickness of 0.5 to 3 mm, especially 2 mm or less, exhibits flame retardancy of V-2 or more in UL94 standard, and has excellent antistatic properties.
Printers, personal computers with molded product thickness of 3 mm or less,
Housings and components for DVD drives, PD drives, floppy disk drives, and storage devices such as DVD drives, PD drives, floppy disk drives, etc., including displays, CRT displays, fax machines, copy machines, word processors, and notebook computers. Especially useful for:

[0086]

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 Styrene-Based Resin A method for preparing 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)
m, gel content 82%) was charged into a stainless steel reaction vessel, and while stirring, glucose, sodium pyrophosphate, and ferrous sulfate dissolved in ion-exchanged water were charged into the reaction vessel. Was raised to 65 ° C. Styrene 29.2 parts, acrylonitrile 10.8
, A mixed solution consisting of 0.2 parts of t-dodecylmercaptan, and an aqueous solution containing 0.4 parts of cumene hydroperoxide and 1.5 parts of potassium oleate were separately dropped continuously for 3 hours and 4 hours, respectively, to carry out polymerization. Was completed. The conversion was in the range of 99%.

The obtained graft copolymer is coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a powder.
A graft copolymer was prepared. The obtained graft copolymer had a graft ratio of 38%. This graft copolymer is a non-graft copolymer composed of 73% of styrene structural units and 27% of acrylonitrile is 16.8.
%. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.25 dl / g.

(A2) Preparation of vinyl copolymer A monomer mixture composed of 72% styrene and 28% acrylonitrile was subjected to suspension polymerization to prepare a vinyl copolymer.
The intrinsic viscosity of the obtained vinyl copolymer in a methyl ethyl ketone solvent was 0.51.

Reference Example 2 (B) Preparation of antistatic polymer 40 parts of caprolactam, 56.3 parts of polyethylene glycol having a number average molecular weight of 2000, and 4.8 of terephthalic acid
Part of antioxidant (“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 heated and stirred for 50 minutes while replacing with nitrogen and flowing a small amount of nitrogen at 260 ° C. to obtain a transparent homogeneous solution. 260 ° C, 0.5mmHg
Polymerization was performed for 3 hours under the following conditions to obtain a transparent polymer. The polymer was discharged in a gut shape on a cooling belt and pelletized to prepare a pellet-like polyetheresteramide.

The obtained polyetheresteramide was placed in a 0.5% orthochlorophenol solution at 25 ° C.
Has a relative viscosity (ηr) of 2.1 and a volume resistivity of 2 × 10 ⁹ Ωcm.

Reference Example 3 (C) Radical Generator Nofumer BC (manufactured by NOF Corporation), which is 2,3-diphenyl-2,3-dimethylbutane, was used (1 minute half-life temperature: 330 ° C.).

Reference Example 4 (D) Phosphorus-based flame retardant Aromatic phosphate PX-200 (manufactured by Daihachi Chemical Co., Ltd.)
It was used.

Examples 1 to 7, Comparative Examples 1 to 4 (A) Rubber-reinforced styrene resin prepared in Reference Examples,
(B) An antistatic resin, (C) a radical generator, and (D) a phosphorus-based flame retardant were mixed at the compounding ratio shown in Table 1, and a mixture with a vent 3
A pellet-shaped polymer was produced by melt-kneading and extruding with a 0 mm φ twin-screw extruder. 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) Flexural modulus: ASTM D790 (3) Deflection temperature under load: ASTM D648 (Load:
1.82 MPa)

(4) 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.

Immediately after molding, the product 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. Measured below.

After molding, the mixture was allowed to stand at 23 ° C. and 50% RH for 100 days, and then the detergent “Mamaroyal” (Lion Corporation) was used.
After washing with an aqueous solution and then sufficiently with distilled water to remove the water on the surface, a room temperature of 23 ° C. and a humidity of 50% were used.
It was measured under an RH atmosphere.

(5) Flame retardancy: A vertical flame retardance test was performed at 1/16 ″ × 1 / according to the evaluation criteria defined in the UL94 standard.
The test was performed on a 2 ″ × 5 ″ combustion test piece. Flame retardancy level is V-
0>V-1>V-2> HB.

Table 2 shows the measurement results.

[0103]

[Table 1]

[0104]

[Table 2]

The following is clear from the results in Table 2. When a small amount of a radical generator is added to a resin composition of the present invention (Examples 1 to 7), or when a small amount of a radical generator and a phosphorus-based flame retardant are used in combination, the flame retardancy is remarkably improved, and the impact strength is increased. It has excellent mechanical properties such as flexural modulus and heat resistance, and 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, heat resistance and permanent antistatic properties.

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

When the compounding amount of the radical generator (C) is 0.01
When the amount is less than 5 parts by weight (Comparative Example 3), the flame retardancy is poor. When the amount of the radical generator (C) exceeds 5 parts by weight (Comparative Example 43), the flame retardancy and heat resistance are poor.

[0109]

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

Claims (13)

[Claims] 1. A rubber-reinforced styrene resin (A) 60 to 99.
(A) resin composition 10 comprising 1% to 40% by weight of a polymer having a volume specific resistance of 10 ¹³ Ωcm or less (B)
(C) radical generator 0.01 to 5 parts by weight per 0 parts by weight
A flame-retardant resin composition characterized by being mixed with parts by weight. 2. The method according to claim 1, wherein the polymer (B) is a polymer containing a poly (alkylene oxide) glycol residue, a quaternary ammonium salt residue, or an alkali metal ionomer residue. Flame retardant resin composition. 3. The flame-retardant resin composition according to claim 1, wherein (B) the polymer is polyetheramide, polyetherester, or polyetheresteramide. 4. The flame-retardant resin composition according to claim 1, wherein the polymer (B) is a quaternary ammonium salt group-containing olefin copolymer. 5. The method according to claim 1, wherein (C) the radical generator has -O-
The flame-retardant resin composition according to any one of claims 1 to 4, wherein the flame-retardant resin composition has one kind of a chemical bond of an O-bond and a -CC- bond. 6. The one-minute half-life of the radical generator (C) is 20.
The flame-retardant resin composition according to claim 1, wherein the temperature is 0 ° C. or higher. 7. The method according to claim 1, wherein the radical generator (C) has the following general formula (1):
The flame-retardant resin composition according to any one of claims 1 to 6, wherein Embedded image (In the above formula, R ^{1 to} R ⁶ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.) 8. The radical generator (C) represented by the following general formula (2)
The flame-retardant resin composition according to any one of claims 1 to 6, wherein Embedded image (In the above formula, R ^{2 to} R ⁵ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.) 9. The radical generator (C) represented by the following general formula (3)
The flame-retardant resin composition according to any one of claims 1 to 6, wherein Embedded image 10. The flame-retardant resin composition according to claim 1, wherein the radical generator (C) has a structure represented by the following general formula (4). Embedded image (In the above formula, R ^{7 to} R ⁹ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms, and these organic residues are substituted with one or more —OOH groups. May be done.) 11. The flame-retardant resin composition according to claim 1, wherein the radical generator (C) is one kind or a mixture of two or more kinds selected from the following general formula (5). Stuff. Embedded image 12. The flame retardant according to claim 1, further comprising (D) 0.1 to 30 parts by weight of a phosphorus-based flame retardant per 100 parts by weight of the resin composition. Resin composition. 13. The flame-retardant resin composition according to claim 12, wherein (D) the phosphorus-based flame retardant is an aromatic phosphate represented by the following general formula (6). Embedded image (In the above formula, R ^{10 to} R ¹⁷ 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. )