JP2007016123A - Flame retardant thermoplastic resin composition and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant thermoplastic resin composition excellent in flame retardancy, sliding properties, heat resistance and antistatic properties, and its molded product. <P>SOLUTION: The flame retardant thermoplastic resin composition is obtained by adding (II) 5-30 parts by weight of an aromatic phosphoric acid ester compound, (III) 3-30 parts by weight of a polyamide elastomer, (IV) 0.1-15 parts by weight of a modified vinyl copolymer having at least one functional group and (V) 1-10 parts by weight of polyolefin wax to (I) 100 parts by weight of a rubber-reinforced styrene-based resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame retardant thermoplastic resin composition excellent in flame retardancy, slidability, heat resistance and antistatic property, and a molded article comprising the same.

  A styrene resin comprising a graft polymer obtained by polymerizing an aromatic vinyl compound such as styrene or α-methylstyrene with a rubber polymer, and a vinyl cyanide compound such as acrylonitrile or methacrylonitrile with the rubber polymer; ABS resin containing a graft copolymer obtained by copolymerizing an aromatic vinyl compound such as styrene or α-methylstyrene is excellent in mechanical strength and molding processability. As semi-engineering plastics with intermediate characteristics, they are widely used for OA equipment and home appliances.

  Since styrene resins (ABS resins are included in styrene resins) are inherently flammable, various flame retardant techniques have been proposed from the viewpoint of safety.

  As a general flame-retarding technology for styrene-based resins, a method of flame-retarding by combining halogen-based flame retardants such as chlorine compounds and bromine compounds with high flame retardancy efficiency and antimony oxide is adopted. However, the flame retardant thermoplastic resin composition obtained by this method has a drawback that a halogen-based flame retardant decomposes and gas is generated during molding or combustion.

  In recent years, in order to overcome the drawbacks of flame retardant thermoplastic resin compositions containing these halogen-based flame retardants, flame retardant thermoplastic resin compositions containing no halogen have been strongly desired.

  As a method for making a thermoplastic resin flame retardant without using a halogen-based flame retardant, a method of adding a phosphorus compound to the resin (for example, see Patent Document 1 and Patent Document 2) has been proposed.

  In addition, ABS resins have the disadvantage that they cannot be used for applications that require strict sliding characteristics because ABS resin molded products wear significantly when they are rubbed against each other or with metals or other resins. Was.

  As a general sliding technology of ABS resin, a method of adding polytetrafluoroethylene or glycerin fatty acid ester wax is employed.

  However, when the slidability is imparted to the flame retardant thermoplastic resin composition obtained by the method described in Patent Document 1 or Patent Document 2 by the method of adding polytetrafluoroethylene, the impact resistance is remarkably reduced. Furthermore, there was a problem such as cost increase.

In addition, when slidability is imparted by adding glycerin fatty acid ester wax, sufficient flame retardancy cannot be obtained, and heat resistance is not only lowered, but also mold contamination during molding and molded product There was a problem that "stickiness" occurred.
JP 59-24736 A JP-A-63-117057

  An object of the present invention is to provide a flame retardant thermoplastic resin composition excellent in flame retardancy, slidability, heat resistance, and antistatic properties, and a molded product comprising the same, by eliminating the drawbacks of the prior art described above. It is in.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the rubber-reinforced styrene resin has a specific amount of each of an aromatic phosphate compound, a polyamide elastomer, a modified vinyl copolymer, and a specific polyolefin wax. It was found that the above-mentioned object can be achieved efficiently by blending, and the present invention has been achieved.

  That is, to achieve the above object, according to the present invention, 5 to 30 parts by weight of the aromatic phosphate compound (II), polyamide elastomer (III) 3 per 100 parts by weight of the rubber-reinforced styrene resin (I) Flame retardancy obtained by adding ~ 30 parts by weight, 0.1 to 15 parts by weight of a modified vinyl copolymer (IV) having at least one functional group and 1 to 10 parts by weight of a polyolefin wax (V) A thermoplastic resin composition is provided.

In the flame-retardant thermoplastic resin composition of the present invention,
The melting point of the polyolefin wax (V) is 50 to 120 ° C.,
The polyolefin wax (V) is low molecular weight polyethylene, polypropylene or a modified compound thereof;
2-8 parts by weight of the polyolefin wax (V) is added,
The polyamide elastomer (IV) is a polyamide elastomer, and
The modified vinyl copolymer (V) is preferably a copolymer obtained by copolymerizing at least aromatic vinyl, vinyl cyanide and methacrylic acid. In these cases, Furthermore, the acquisition of an excellent effect can be expected.

  Moreover, the molded article of the present invention is characterized by comprising the above-mentioned flame retardant thermoplastic resin composition.

  According to the present invention, as described below, not only flame retardancy, slidability, heat resistance and antistatic properties, but also good impact resistance, mold contamination during molding and “stickiness” of the molded product. Excellent flame retardant thermoplastic resin compositions and molded articles comprising the same can be obtained.

  The present invention will be specifically described below.

    The present invention relates to 100 parts by weight of a rubber-reinforced styrene resin (I), 5 to 30 parts by weight of an aromatic phosphate ester compound (II), 3 to 30 parts by weight of a polyamide elastomer (III), and at least one functional group. A flame-retardant thermoplastic resin composition comprising 0.1 to 15 parts by weight of a modified vinyl copolymer (IV) having a group and 1 to 10 parts by weight of a polyolefin wax (V).

  Examples of the rubber-reinforced styrene resin in the present invention include an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), and other copolymerizable monomers with respect to the rubber polymer (a). A graft copolymer (A) obtained by graft copolymerization of at least one monomer selected from vinyl monomers (d), an aromatic vinyl monomer (b), and a vinyl cyanide monomer. And a composition comprising a vinyl (co) polymer (B) comprising at least one monomer selected from the monomer (c) and other copolymerizable vinyl monomers (d). It is done.

  In the rubber-reinforced styrene resin in the present invention, the rubbery polymer (a) used for the graft copolymer (A) is not particularly limited, but diene rubber, acrylic rubber, ethylene rubber, and the like can be used. . Specific examples include polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl methacrylate), poly (butyl acrylate-methyl methacrylate). ), Poly (butadiene-ethyl acrylate), ethylene-propylene rubber, ethylene-propylene-diene rubber, poly (ethylene-isoprene), poly (ethylene-methyl acrylate), and the like. These rubbery polymers (a) are used in one kind or a mixture of two or more kinds. Among these rubbery polymers (a), polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), and ethylene-propylene rubber are all preferably used in terms of impact resistance.

  In the rubber-reinforced styrene resin in the present invention, the weight average particle diameter of the rubbery polymer (a) constituting the graft copolymer (A) is not particularly limited, but is in the range of 0.1 to 0.5 μm. It is preferable that If it is this range, the flame-retardant thermoplastic resin composition obtained will have a good balance between impact strength and moldability.

  In the rubber-reinforced styrene resin in the present invention, the aromatic vinyl monomer (b) used for the graft copolymer (A) and the vinyl (co) polymer (B) is not particularly limited, Specific examples include styrene, α-methyl styrene, orthomethyl styrene, paramethyl styrene, para-t-butyl styrene, halogenated styrene, and the like, and one or more can be used. Of these, styrene and α-methylstyrene are preferable from the viewpoint of balance of mechanical properties, productivity, economy, and the like, and styrene is particularly preferable.

  In the rubber-reinforced styrene resin in the present invention, the vinyl cyanide monomer (c) used for the graft copolymer (A) and the vinyl (co) polymer (B) is not particularly limited. Examples thereof include acrylonitrile and methacrylonitrile, and can be used alone or in combination of two or more. Of these, acrylonitrile is preferable in terms of impact resistance.

  In the rubber-reinforced styrene-based resin in the present invention, there are no particular restrictions on the other copolymerizable vinyl monomers (e) used for the graft copolymer (A) and the vinyl-based (co) polymer (B). Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth Acrylates having 1 to 6 carbon atoms or substituted alkyl groups such as n-hexyl acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate and 2-chloroethyl (meth) acrylate, and / Or maleimidation of methacrylic acid ester, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc. Products, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic acid anhydrides such as maleic anhydride, and copolymerizable vinyl compounds typified by unsaturated amide compounds such as acrylamide. Or 2 or more types can be used.

  In the rubber-reinforced styrene resin in the present invention, the monomer composition used for the graft copolymer (A) preferably contains 10 to 90% by weight of the aromatic vinyl monomer (b). More preferably, it is 20 to 80% by weight. The graft copolymer (A) can contain 0 to 50% by weight, preferably 0 to 40% by weight, of the vinyl cyanide monomer (c) as necessary. Furthermore, the graft copolymer may contain 0 to 90% by weight, preferably 0 to 80% by weight, of another copolymerizable vinyl monomer (d) as necessary. Such a composition is preferable because the moldability and impact resistance are balanced.

  In the present invention, in the rubber-reinforced styrene resin, the content of the rubber polymer (a) in the graft copolymer (A) is not particularly limited, but is preferably 20 to 80 parts by weight. If it is less than 20 parts by weight, the impact strength of the obtained flame-retardant thermoplastic resin composition is lowered. More preferably, it is 35 to 60 parts by weight. Note that the monomer mixture blended in the graft copolymer (A) does not have to be all grafted by bonding to the rubber polymer (a). They may be bonded together and included as an ungrafted polymer. However, the graft ratio is preferably 10 to 100%, particularly preferably 20 to 50%.

  In the present invention, in the rubber-reinforced styrene resin, the aromatic vinyl monomer (b), the vinyl cyanide monomer (c) constituting the vinyl (co) polymer (B), and, if necessary, The composition of the other copolymerizable vinyl monomer (d) is not particularly limited, but is preferably an aromatic vinyl monomer (in view of balancing moldability and impact resistance). b) 10 to 90% by weight, vinyl cyanide monomer (c) 0 to 50% by weight, and other copolymerizable vinyl monomer (d) 0 to 90% by weight. More preferably, the aromatic vinyl monomer (b) is 20 to 80% by weight, the vinyl cyanide monomer (c) is 0 to 40% by weight, and other copolymerizable vinyl monomers (d). 0 to 80% by weight.

  In the present invention, in the rubber-reinforced styrene resin, the reduced viscosity (ηsp / c) of the vinyl (co) polymer (B) is not particularly limited, but is preferably in the range of 0.1 to 0.8 dl / g. . In other cases, the impact resistance is lowered, or the melt viscosity is increased and the moldability tends to be deteriorated. More preferably, it is the range of 0.3-0.7 dl / g.

  In the present invention, a plurality of types of vinyl (co) polymers (B) can be used in the rubber-reinforced styrene resin.

  In the present invention, in the rubber-reinforced styrene resin, there is no particular limitation on the method for producing the graft copolymer (A) and the vinyl (co) polymer (B), and bulk polymerization, solution polymerization, suspension polymerization, and emulsification are performed. Any of polymerization and the like may be used. There is no particular limitation on the monomer charging method, and any method of initial batch charging, continuous charging of part or all of the monomer, or partial charging of part or all of the monomer may be used. .

  The mixing ratio of the graft copolymer (A) and the vinyl (co) polymer (B) constituting the rubber-reinforced styrene resin (I) in the flame retardant thermoplastic resin composition of the present invention is preferably It is a ratio of 10 to 60 parts by weight of the graft copolymer (A) and 40 to 90 parts by weight of the vinyl (co) polymer (B). If the graft copolymer (A) is less than 10 parts by weight or the vinyl (co) polymer (B) exceeds 90 parts by weight, the impact strength may be lowered. On the other hand, when the graft copolymer (A) exceeds 60 parts by weight, the melt viscosity is increased, the moldability is deteriorated, and the flame retardancy is sometimes lowered. The ratio is preferably 20 to 50 parts by weight of the graft copolymer (A) and 50 to 80 parts by weight of the vinyl (co) polymer (B).

  The aromatic phosphate ester compound (II) used in the flame-retardant thermoplastic resin composition of the present invention is preferably represented by the following general formula (1).

  First, the structure of the flame retardant represented by the formula (1) will be described.

  In the formula (1), R1 to R8 represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms.

  Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-isopropyl and neopentyl. , Tert-pentyl group, 2-isopropyl, neopentyl, tert-pentyl group, 3-isopropyl, neopentyl, tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group, etc., hydrogen, methyl group, ethyl group Are preferable, and hydrogen is particularly preferable.

  Ar1, Ar2, Ar3, and Ar4 represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Specific examples include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, naphthyl group, indenyl group, anthryl group, etc., but phenyl group, tolyl group, xylyl group, cumenyl group, naphthyl group are preferable. In particular, a phenyl group, a tolyl group, and a xylyl group are preferable.

  Y in the formula represents a direct bond, O, S, SO2, C (CH3) 2, CH2, 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, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

  The content of the aromatic phosphate ester compound (II) is preferably 1 to 30 parts by weight, more preferably 5 parts per 100 parts by weight in total of the graft copolymer (A) and the vinyl copolymer (B). -30 parts by weight. If the content of the aromatic phosphate ester compound (II) is less than 5 parts by weight, the flame-retardant thermoplastic resin obtained is insufficient in flame retardancy, and if it exceeds 30 parts by weight, the slidability and impact resistance are poor. descend.

  Examples of the polyamide elastomer (III) in the flame-retardant thermoplastic resin composition of the present invention include grafts or blocks by reaction with a polyamide-forming component (a) having 6 or more carbon atoms and poly (alkylene oxide) glycol (b). A copolymer is mentioned. Here, as the amide-forming component (a) having 6 or more carbon atoms, specifically, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid Aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, or lactams such as caprolactam, enantolactam, capryllactam, laurolactam, hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexa Mention may be made of nylon salts such as methylenediamine-isophthalate. Examples of poly (alkylene oxide) glycol (b) include polyethylene oxide glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly ( Hexamethylene oxide) glycol, ethylene oxide and propylene oxide block or random copolymer, ethylene oxide and tetrahydrofuran block or random copolymer, and the like are used. 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 rigidity, and more preferably 300 to 4000. Further, if necessary, both ends of the component (b) may be aminated or carboxylated.

  In the flame-retardant thermoplastic resin composition of the present invention, the polyamide elastomer (III) is more preferably a polyetheresteramide.

    In the flame-retardant thermoplastic resin composition of the present invention, the bond between the polyamide-forming component (a) having 6 or more carbon atoms and the poly (alkylene oxide) glycol component (b) in the polyamide elastomer (III) is usually an ester. Although it is a bond or an amide bond, it is not particularly limited thereto. It is also possible to use a third component such as dicarboxylic acid (c) or diamine (d) as a reaction component of both components. In this case, the dicarboxylic acid component (c) is terephthalate having 4 to 20 carbon atoms. Acid, isophthalic acid, phthalic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acid such as sodium 3-sulfoisophthalate, 1,4 -Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, aliphatics such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanediic acid Dicarboxylic acids, in particular 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dodecanedi But polymerizable, color tone, from the viewpoint of physical properties. On the other hand, as the diamine component (d), aromatic, alicyclic and aliphatic diamines are used, and among them, the aliphatic diamine hexamethylene diamine is preferable from the viewpoints of polymerizability, color tone and physical properties.

  The method for polymerizing the polyamide elastomer (III) in the flame retardant thermoplastic resin composition of the present invention is not particularly limited. For example, aminocarboxylic acid or lactam (a) and dicarboxylic acid (c) are reacted in an equimolar ratio. , A method of reacting poly (alkylene oxide) glycol (b) under vacuum with a polyamide prepolymer having carboxylic acid groups at both ends, and the compounds (a), (b) and (c) above. A method of preparing a carboxylic acid-terminated polyamide prepolymer by charging in a reaction vessel and performing a pressure reaction at high temperature in the presence or absence of water, and then proceeding polymerization under normal pressure or reduced pressure, or the above A known method such as a method in which the compounds of (a), (b) and (c) are simultaneously charged into a reaction vessel and melt polymerization is performed, and then the polymerization is advanced at once under high vacuum is adopted. It is possible.

  The content of the polyamide elastomer (III) in the flame retardant thermoplastic resin composition of the present invention is such that the flame retardant and the vinyl copolymer (A) and the graft copolymer (B) are 100 parts by weight in total. 3-30 weight part is preferable from the point of balance with antistatic property, More preferably, it is 5-20 weight part. When the content of the polyamide elastomer (III) is less than 3 parts by weight, the anti-static property of the obtained flame retardant thermoplastic resin composition is insufficient, and when it exceeds 30 parts by weight, the flame retardancy may be lowered.

  The modified vinyl copolymer (IV) in the flame retardant thermoplastic resin composition of the present invention has a structure obtained by copolymerizing two or more vinyl monomers, and has a carboxyl group in the molecular chain. Those having at least one functional group of a group, an epoxy group, an amino group, and an amide group are preferred. Although there is no limitation in particular as content of these functional groups, 0.1 to 20 weight% is preferable, More preferably, it is 0.1 to 15 weight%. If it is less than 0.1% by weight, the effect of improving impact resistance is not sufficient, and if it exceeds 20% by weight, it may be difficult to produce a modified vinyl polymer or gelation may occur due to self-reaction. The method for introducing at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, and an amide group into the modified vinyl copolymer (IV) is not particularly limited. Examples thereof include a method of copolymerizing a vinyl monomer having a functional group, and a method of copolymerizing a predetermined vinyl monomer using the above-described polymerization initiator having a functional group or a chain transfer agent.

    Specific examples of the vinyl monomer having the functional group, the polymerization initiator, and the chain transfer agent are as follows. Examples of vinyl monomers include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride or itaconic acid, epoxy groups such as glycidyl acrylate, glycidyl methacrylate or glycidyl itaconate. Monomers having amino acids, aminoalkyl ester derivatives of (meth) acrylic acid such as aminoethyl acrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, vinylamine derivatives such as N-acetylvinylamine, methallylamine, etc. Monomers having an amino group such as allylamine derivatives or aminostyrene, and monomers having an amide group such as acrylamide and N-methylmethacrylamide.

  In the flame-retardant thermoplastic resin composition of the present invention, the modified vinyl copolymer (IV) is more preferably a copolymer obtained by copolymerizing at least aromatic vinyl, vinyl cyanide and methacrylic acid. preferable.

    The flame retardant thermoplastic resin composition of the present invention preferably contains a polymerization initiator. Examples of the polymerization initiator include initiators having a carboxyl group such as γ, γ′-azobis (γ-cyanovaleric acid) or peroxysuccinic acid, and α, α′-azobis (γ-amino-α, γ- And initiators having an amino group such as divaleronitrile) or p-aminobenzoyl peroxide.

  The flame retardant thermoplastic resin composition of the present invention preferably contains a chain transfer agent. Examples of chain transfer agents include chain transfer agents having a carboxyl group such as mercaptopropion, 4-mercaptobenzoic acid or thioglycolic acid, mercaptomethylamine, N- (β-mercaptoethyl) -N-methylamine, bis- Examples include chain transfer agents having an amino group such as (4-aminophenyl) disulfide or mercaptoaniline.

  In the flame-retardant thermoplastic resin composition of the present invention, the polymerization method for copolymerizing the modified vinyl copolymer (IV) is not particularly limited, but suspension polymerization, bulk polymerization, emulsion polymerization, solution polymerization, etc. This method is preferred.

  The reduced viscosity of the modified vinyl copolymer (IV) in the flame retardant thermoplastic resin composition of the present invention has a range of 0.2 dl / g to 1.5 dl / g from the viewpoint of moldability and impact resistance. preferable. More preferably, it is the range of 0.4 dl / g-1.0 dl / g. If the reduced viscosity of the modified vinyl copolymer (IV) is less than 0.2 dl / g, the resulting thermoplastic resin composition may not have sufficient impact resistance improving effect, and exceeds 1.5 dl / g. And moldability may be reduced.

  The content of the modified vinyl copolymer (IV) in the flame retardant thermoplastic resin composition of the present invention is 0.1 to 15 parts by weight from the viewpoint of balance between flame retardancy, mechanical strength and moldability. Is preferable, and the range of 1.0 to 10 parts by weight is more preferable. If the content of the modified vinyl copolymer (IV) is less than 0.1 part by weight, the impact resistance improving effect of the obtained flame-retardant thermoplastic resin composition is not sufficiently exhibited, and 15 parts by weight When it exceeds, it exists in the tendency for a flame retardance and a moldability to fall.

  Examples of the polyolefin wax (V) in the flame-retardant thermoplastic resin composition of the present invention include low molecular weight polyethylene, polypropylene, and modified compounds thereof. The polyolefin wax (V) is particularly preferably low molecular weight polyethylene, polypropylene, or a modified compound thereof.

    In the flame-retardant thermoplastic resin composition of the present invention, the polyolefin wax (V) is obtained, for example, by a low-pressure polymerization method using a Ziegler catalyst or the like, or obtained by a high-pressure method, or a low-pressure polymerization method. And a polyolefin-based wax obtained by decomposing and reducing the molecular weight of a high-molecular-weight polyolefin obtained by a high-pressure polymerization method, and a modified polyolefin-based wax. Denaturation is oxidative modification, and the degree of modification is determined by the degree of oxidation obtained by a titration test method using potassium hydroxide.

  In the flame-retardant thermoplastic resin composition of the present invention, when polytetrafluoroethylene, which is a general sliding agent other than the polyolefin wax (V), is added, the resulting flame-retardant thermoplastic resin composition There is a problem in that the impact resistance of the resin significantly decreases and the cost increases.

  In addition, when glycerin fatty acid ester wax is added, the flame retardancy and heat resistance of the resulting flame retardant thermoplastic resin composition are reduced, and mold contamination during molding and stickiness on the surface of the molded product occur. To do.

  Moreover, in the thermoplastic resin composition of the present invention, when a general sliding agent other than the polyolefin wax (V) is used in order to obtain good sliding properties, the effect of improving sliding properties is small. Therefore, it is necessary to increase the amount of addition, which is not preferable from the viewpoints of flame retardancy, balance of physical properties, cost, and mold contamination.

  In the flame-retardant thermoplastic resin composition of the present invention, the melting point of the polyolefin wax (V) is preferably in the range of 50 to 120 ° C. from the viewpoint of mold fouling and sliding properties. When the melting point of the polyolefin wax (V) is less than 50 ° C., problems such as mold contamination occur, and when it exceeds 120 ° C., the slidability tends to decrease.

    In the flame retardant thermoplastic resin composition of the present invention, the content of the polyolefin wax (V) is flame retardant with respect to a total of 100 parts by weight of the vinyl copolymer (A) and the graft copolymer (B). 1 to 10 parts by weight is preferable from the viewpoint of balance between the property and the sliding property, and more preferably 2 to 8 parts by weight. When the content of the polyolefin wax (V) is less than 1 part by weight, the slidability of the obtained flame-retardant thermoplastic resin composition is insufficient, and when it exceeds 10 parts by weight, the flame retardancy may be lowered. .

  The method for producing the flame-retardant thermoplastic resin composition of the present invention is not particularly limited, and the thermoplastic resin (I), the aromatic phosphate compound (II), the polyamide elastomer (III), and the modified vinyl copolymer (IV) and the polyolefin wax (V) can be produced by, for example, melt-kneading with a Banbury mixer, roll, extruder, kneader or the like.

  In addition, the flame retardant thermoplastic resin composition of the present invention is further improved in performance as a molding resin composition by blending various thermoplastic resins and elastomers within a range not impairing the object of the present invention. be able to.

  In addition, the flame retardant thermoplastic resin composition of the present invention is optionally provided with a hindered phenol-based, sulfur-containing compound-based, phosphorus-containing organic compound-based antioxidant, phenol-based, acrylate-based, etc. Agents, UV absorbers such as benzotriazoles, benzophenones, and succinates, various stabilizers such as light stabilizers such as organic nickels and hindered amines, lubricants such as metal salts of higher fatty acids, higher fatty acid amides, phthalic acid Plasticizers such as esters and phosphate esters, flame retardants such as halogens and phosphorus (red phosphorus, phosphate esters, etc.), flame retardant aids such as antimony trioxide and antimony pentoxide, carbon black, pigments and Dye etc. can also be added.

  Furthermore, various reinforcing agents and fillers can also be added to the flame retardant thermoplastic resin composition of the present invention.

    The flame-retardant thermoplastic resin composition of the present invention can be a molded article.

    The flame retardant thermoplastic resin composition excellent in flame retardancy, slidability, heat resistance and antistatic property of the present invention is used for injection molding, extrusion molding, blow molding, vacuum molding, compression molding, gas assist molding, etc. It can be molded by a known method currently used for molding thermoplastic resins, and is not particularly limited.

  The flame retardant thermoplastic resin composition of the present invention is not only flame retardant, but also has excellent heat resistance, slidability, and antistatic properties, making it an electric / electronic component, OA equipment, home appliance, miscellaneous goods Etc. and can be suitably used as their parts.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited thereby. In Examples and Comparative Examples, unless otherwise specified, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  First, the analysis method of the characteristic of a flame-retardant thermoplastic resin composition is described below.

(1) Weight average rubber particle diameter According to the sodium alginate method described in “Rubber Age Vol. 88, pp. 484-490 (Rubber Age Vol. 88 p. 484-490 (1960) by E. Schmidt, PH Biddison)” Asked. That is, utilizing the fact that the diameter of the polybutadiene particles to be creamed differs depending on the concentration of sodium alginate, the particle size of 50% cumulative weight fraction was determined from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration.

(2) Graft rate Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 3 hours. This solution was centrifuged at 8800 rpm for 10 minutes, and the insoluble matter was collected by filtration. This insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the weight (n) was measured. The graft ratio was calculated from the following formula.

Graft ratio (%) = {[(n) − (m) × L] / [(m) × L]} × 100
Here, L is the rubber content of the graft copolymer.

(3) Reduced viscosity ηsp / c
200 ml of acetone was added to 1 g of the sample and refluxed for 3 hours. The solution was centrifuged at 8800 rpm for 10 minutes, and the insoluble matter was filtered. The filtrate was concentrated with a rotary evaporator, and the precipitate (acetone soluble matter) was dried under reduced pressure at 60 ° C. for 5 hours, adjusted to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and then ηsp / c using an Ubbelohde viscometer. Was measured.

(4) Flame retardancy The flame retardancy was evaluated according to the evaluation standard defined in UL94 for the 1.5 mm thick flame retardant evaluation test piece obtained by injection molding. The flame retardancy level decreases in the order of V-0, V-1, V-2, and HB.

(5) Static friction coefficient It measured using the automatic friction and abrasion analyzer DFPM-SS type | mold by Kyowa Interface Science. Test pieces having a length of 60 mm × width of 50 mm × thickness of 3 mm were prepared by injection molding, and the static friction coefficient with copy paper (NBS Ricoh Co., Ltd., My Recycle Paper New) was measured. The measurement was performed under the conditions of a load of 100 g (load stress of 0.0098 MPa), a stroke of 50 mm, and a speed of 0.1 mm / sec in an environment of a temperature of 23 ± 1 ° C. and a humidity of 50 ± 5 ° C.

[Decision] <0.15: ◎ (Pass)
0.15-0.30: ○ (pass)
> 0.30: x (failed).

(6) Izod impact strength The Izod impact strength was measured under the conditions of 12.7 mm notch and 23 ° C., in accordance with ASTM D256.

(7) Deflection temperature under load It was measured under the conditions of 6.4 mm and 1.82 MPa in accordance with ASTM D648.

(8) Melt flow rate The melt flow rate was evaluated according to ISO 1133 (temperature: 220 ° C., load: 98 N).

(9) Charge voltage (electrostatic dissipative performance), charge voltage decay half life 80-50 ° C. IS-50A molding manufactured by Toshiba Corporation in which the pellet of the resin composition dried for 3 hours in hot air drying is set at a cylinder temperature of 230 ° C. It was filled in the machine and measured with a static Honest meter (manufactured by Shishido) on a square plate molded product (40 mm (W) × 50 mm (L) × 3 mm (t)) obtained by injection molding. The distance between the molded product and the application electrode was 15 mm, the distance between the detection electrode and the detection electrode was 10 mm, a voltage of 8 kV was applied for 1 minute, and the charged voltage at that time was read. For the half-life of the charged voltage decay, application was stopped and the time until the charged voltage was halved was read. It can be said that the lower the charged voltage and the shorter the half-life of the charged voltage, the better the electrostatic dissipation performance.

[Reference Example 1] Production method of graft copolymer (A) In a reactor purged with nitrogen, 120 parts of pure water, 0.5 part of glucose, 0.5 part of sodium pyrophosphate, 0.005 part of ferrous sulfate and 60 parts (in terms of solid content) of polybutadiene latex (rubber particle diameter 0.3 μm, gel content 85%) was charged, and the temperature in the reactor was raised to 65 ° C. while stirring. When the internal temperature reached 65 ° C., a monomer mixture (30 parts of styrene and 10 parts of acrylonitrile) and a mixture of 0.3 part of t-dodecyl mercaptan were continuously added dropwise over 5 hours. Simultaneously with the monomer, an aqueous solution consisting of 0.25 parts cumene hydroperoxide, 2.5 parts potassium oleate and 25 parts pure water was continuously dropped over 7 hours to complete the monomer reaction. .

  The obtained styrene copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain graft copolymer A-1. The graft ratio of this styrene-based graft copolymer A-1 was 35%, and the ηsp / c of the resin component was 0.35 dl / g.

[Reference Example 2] Production method of vinyl (co) polymer (B) A stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade was charged with 20% by weight of methyl methacrylate and 80% by weight of acrylamide. After adding a solution obtained by dissolving 0.05 part of the copolymer in 165 parts of ion-exchanged water, 400 r. p. The system was replaced with nitrogen gas while stirring at m.

  Next, 30 parts of acrylonitrile, 5 parts of styrene, 0.46 part of t-dodecyl mercaptan, 0.39 part of 2,2′-azobis (2,4-dimethylvaleronitrile) and 0,2,2′-azobisisobutylnitrile .05 parts of the monomer mixture was added and the temperature was raised to 58 ° C. to initiate polymerization. After 15 minutes from the start of polymerization, 65 parts of styrene was added over 110 minutes from a supply pump provided at the top of the autoclave. During this time, the reaction temperature was raised to 65 ° C. After completing the addition of styrene to the reaction system, the temperature was raised to 100 ° C. over 50 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried according to the usual method to obtain a vinyl (co) polymer B-1. The vinyl (co) polymer B-1 had a ηsp / c of 0.53 dl / g.

[Reference Example 3] Aromatic phosphate ester compound (II)
<II-1> “PX-200” (manufactured by Daihachi Chemical Industry Co., Ltd.)
[Reference Example 4] Polyamide elastomer (III)
Helical 40.0 parts caprolactam, 53.1 parts polyethylene glycol with a number average molecular weight of 1000, and 9.2 parts terephthalic acid together with 0.2 parts "Irganox 1098" (antioxidant) and 0.1 part antimony trioxide catalyst After charging into a reaction vessel equipped with a ribbon stirring blade, replacing with nitrogen and heating and stirring at 260 ° C. for 1 hour to make a transparent uniform solution, polymerization was conducted for 4 hours under the conditions of 260 ° C. and 0.5 mmHg or less. A transparent polymer was obtained. The obtained polymer was discharged in a strand shape and cut to obtain polyether ester amide IV-1 on the pellet.

[Reference Example 5] Modified vinyl copolymer (IV)
70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid were subjected to suspension polymerization to obtain a bead-like modified vinyl copolymer IV-1. The reduced viscosity of the modified vinyl copolymer was 0.55 dl / g.

[Reference Example 6] Polyolefin wax (V)
<V-1> Arrow wax, melting point: 78 ° C. (manufactured by Yasuhara Chemical Co., Ltd.)
<V-2> Neowax L, melting point: 110 ° C. (manufactured by Yasuhara Chemical Co., Ltd.)
[Reference Example 7] Glycerin fatty acid ester wax (VI)
<VI-1> Riquemar B100 (Riken Vitamin Co., Ltd.)
[Examples 1 to 8]
Graft copolymer (A), vinyl (co) polymer (B), aromatic phosphate compound (II), polyamide elastomer (III), modified vinyl copolymer (IV) shown in Reference Examples And polyolefin wax (V) were blended at the blending ratios shown in Table 1, respectively, and melt-kneaded and extruded using a vented 30 mmφ twin screw extruder (Ikegai PCM-30) to form pellets A flame retardant thermoplastic resin composition was produced. Then, using an injection molding machine, a test piece was molded at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. The test pieces were measured for physical properties under the above conditions, and the results are shown in Table 1.

    In Examples 1 to 8, the rubber-reinforced styrene resin corresponds to the graft copolymer (A) and the vinyl (co) polymer (B), and the aromatic phosphate compound is aromatic phosphate. This corresponds to the ester compound (II).

[Comparative Examples 1 to 11]
Graft copolymer (A), vinyl (co) polymer (B), aromatic phosphate ester compound (II), polyamide elastomer (III), modified vinyl copolymer (IV) shown in Reference Examples, Polyolefin wax (V) and higher fatty acid ester wax (VI) were mixed at the blending ratios shown in Table 2, and the physical properties of the test pieces obtained by molding in the same manner as in the examples were measured. The measurement results are also shown in Table 2.

  From the results of Tables 1 and 2, the following is clear.

    All of the flame-retardant thermoplastic resin compositions (Examples 1 to 8) of the present invention were excellent in flame retardancy, slidability, heat resistance and antistatic properties.

  When the compounding amount of the vinyl (co) polymer (B) exceeds 90 parts by weight (Comparative Example 1), the impact resistance is inferior.

  On the other hand, when the amount of the graft copolymer (A) exceeds 60 parts by weight (Comparative Example 2), the molding processability and flame retardancy are poor.

  When the amount of the aromatic phosphate compound (II) added is less than 5 parts by weight (Comparative Example 3), the flame retardancy is inferior, and when it exceeds 30 parts by weight (Comparative Example 4), the slidability and impact resistance are increased. Inferior to sex.

  Those having a polyamide elastomer (III) of less than 3 parts by weight (Comparative Example 5) are inferior in antistatic properties of the obtained molded product, and those having a polyamide elastomer (III) in excess of 30 parts by weight (Comparative Example 6) are inferior in flame retardancy.

  When the modified vinyl copolymer (IV) is less than 0.1 parts by weight (Comparative Example 7), the resulting molded article is inferior in impact resistance, and when it exceeds 15 parts by weight (Comparative Example 8) is flame retardant. Inferior in moldability and moldability.

  When the polyolefin wax (V) is less than 1 part by weight (Comparative Example 9), the resulting molded article has poor slidability, and when it exceeds 10 parts by weight (Comparative Example 10), the flame retardancy is poor.

  What added the glycerol fatty acid ester type wax as a sliding agent (Comparative Example 11) is inferior in the flame retardance and heat resistance of the obtained molded article.

Claims (7)

Modification with aromatic phosphate ester compound (II) 5-30 parts by weight, polyamide elastomer (III) 3-30 parts by weight, and at least one functional group based on 100 parts by weight of rubber-reinforced styrene resin (I) A flame retardant thermoplastic resin composition comprising 0.1 to 15 parts by weight of a vinyl copolymer (IV) and 1 to 10 parts by weight of a polyolefin wax (V). The flame retardant thermoplastic resin composition according to claim 1, wherein the polyolefin wax (V) has a melting point of 50 to 120 ° C. The flame retardant thermoplastic resin composition according to claim 1 or 2, wherein the polyolefin wax (V) is low molecular weight polyethylene, polypropylene, or a modified compound thereof. The flame-retardant thermoplastic resin composition according to any one of claims 1 to 3, wherein 2 to 8 parts by weight of the polyolefin wax (V) is added. The flame retardant thermoplastic resin composition according to any one of claims 1 to 4, wherein the polyamide elastomer (III) is a polyether ester amide. The flame retardant according to any one of claims 1 to 5, wherein the modified vinyl copolymer (IV) is a copolymer obtained by copolymerizing at least aromatic vinyl, vinyl cyanide and methacrylic acid. Thermoplastic resin composition. The molded article which consists of a flame-retardant thermoplastic resin composition of any one of Claims 1-6.