JP2019112554A - Polytetrafluoroethylene-containing reinforcement agent and thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having improved impact resistance without impairing the appearance of a molded product while maintaining mechanical properties such as strength and rigidity, and the present inventors contain polytetrafluoroethylene. Invented a fortifier. SOLUTION: A polytetrafluoroethylene-containing fortifier (A) obtained by mixing a core-shell type reinforcing agent aqueous dispersion (A1) and a polytetrafluoroethylene aqueous dispersion (A2) and recovering the powder, and a polytetrafluoroethylene-containing fortifier (A). This can be solved by a thermoplastic resin composition comprising the thermoplastic resin (B). [Selection diagram] None

Description

  The present invention relates to a polytetrafluoroethylene-containing reinforcing agent and a thermoplastic resin composition having improved impact resistance without losing the appearance of a molded article while maintaining mechanical properties such as strength and rigidity.

  Thermoplastic resins are widely used in the fields of automotive parts, electrical and electronic parts, and other precision equipment parts because they are excellent in ease of processing, mechanical properties, and other physical and chemical properties. However, the improvement is desired because the impact resistance strength is low.

  Patent Document 1 proposes a method of blending a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene having a particle diameter of 10 μm or less and a rubbery organic polymer with a thermoplastic resin.

  In Patent Document 2, a polytetrafluoroethylene-containing mixed powder consisting of polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer, and a rubbery polymer having an epoxy group are blended in a thermoplastic polyester resin. A method has been proposed.

Unexamined-Japanese-Patent No. 2001-261966 JP, 2000-290478, A

  In Patent Document 1, after mixing a rubber aqueous dispersion obtained by reacting glycidyl methacrylate with a silicone / acrylic composite rubber aqueous dispersion and a polytetrafluoroethylene-based particle dispersion, an aqueous dispersion obtained by dripping reaction of methyl methacrylate is used. Although a method for producing a polytetrafluoroethylene-containing mixed powder is described, there is a problem that when the thermoplastic resin composition is used, dispersion failure of the rubber tends to occur and appearance defect tends to occur.

  According to the method described in Patent Document 2, when a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer is blended in a thermoplastic polyester resin, orange peel is formed in a molded body There is a problem that (yuzu skin) occurs.

  An object of the present invention is to obtain a resin composition having improved impact resistance without impairing the appearance of a molded article while maintaining mechanical properties such as strength and rigidity.

  The present invention relates to a polytetrafluoroethylene-containing toughener (A) obtained by powder recovery by mixing a core-shell type toughener aqueous dispersion (A1) and a polytetrafluoroethylene aqueous dispersion (A2), and The present invention relates to a thermoplastic resin composition comprising the reinforcing agent (A) and a thermoplastic resin (B).

  According to the polytetrafluoroethylene-containing toughening agent and the thermoplastic resin composition of the present invention, a resin composition having improved impact resistance without impairing the appearance of a molded article while maintaining mechanical properties such as strength and rigidity. You can get

(Core-shell reinforcing agent aqueous dispersion (A1))
The core-shell reinforcing agent aqueous dispersion (A1) which can be used for the polytetrafluoroethylene-containing reinforcing agent (A) of the present invention grafts a vinyl monomer (a2) to a rubbery polymer (a1) It can be obtained by polymerization.

(Rubber polymer (a1))
The rubbery polymer (a1) is not particularly limited, and the polydiene rubbery polymer (a1-1), the polyalkyl (meth) acrylate rubbery polymer (a1-2), and the polyorganosiloxane rubber A high molecular weight polymer (a1-3) etc. can be used.

<Polydiene rubber polymer (a1-1)>
The polydiene rubber polymer (a1-1) is required to contain a diene structural unit. Moreover, you may have another vinyl monomer structural unit as needed. In particular, a polymer having a structural unit having a glass transition temperature of −20 ° C. or less is preferable. The structural units can be used alone or in combination of two or more.

  Although it does not specifically limit as a monomer (diene type monomer) used as the raw material of a diene structural unit, Diene type monomers, such as butadiene and isoprene, for example, 1, 3- butadiene are mentioned.

  As a monomer used as the raw material of another vinyl monomer structural unit, For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , Monofunctional monomers such as stearyl acrylate, t-butyl acrylate, styrene and acrylonitrile; divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, Multifunctional monomers such as pentaerythritol tetraacrylate are mentioned. One of these may be used alone, or two or more may be used in combination. Among these, from the viewpoint of polymerization stability of emulsion polymerization, alkyl acrylates having 2 to 8 carbon atoms and / or styrene are preferable, alkyl acrylates having 3 to 6 carbon atoms and / or styrene are more preferable, butyl acrylate and And / or styrene is particularly preferred.

  The polydiene rubber-like polymer (a1-1) contains 70 mass% or more of diene constitutional units, when the total monomer units constituting the polydiene rubber-like polymer (a1-1) is 100 mass% It is preferable that 80 mass% or more is contained, and 90 mass% or more is more preferable. When 70 mass% or more of diene structural units are contained, the impact resistance of the composition using the polytetrafluoroethylene-containing toughening agent of the present invention for a thermoplastic resin is improved.

<Polyalkyl (meth) acrylate rubbery polymer (a1-2)>
The polyalkyl (meth) acrylate rubbery polymer (a1-2) needs to contain an alkyl (meth) acrylate structural unit. Moreover, you may have another vinyl monomer structural unit as needed. In particular, a polymer having a structural unit having a glass transition temperature of −20 ° C. or less is preferable. The structural units can be used alone or in combination of two or more.

  The monomer (alkyl (meth) acrylate monomer) which is a raw material of the alkyl (meth) acrylate structural unit is not particularly limited, and, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate And 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl acrylate and t-butyl acrylate. One of these may be used alone, or two or more may be used in combination. Among these, from the viewpoint of polymerization stability of emulsion polymerization, alkyl acrylates having 2 to 8 carbon atoms are preferable, alkyl acrylates having 3 to 6 carbon atoms are more preferable, and butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.

  Examples of monomers to be raw materials of other vinyl monomer structural units include monofunctional monomers such as styrene and acrylonitrile; allyl (meth) acrylate, divinyl benzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, Polyfunctional monomers such as triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and the like can be mentioned. One of these may be used alone, or two or more may be used in combination.

  When the polyalkyl (meth) acrylate rubber-like polymer (a1-2) makes all the monomer units which constitute a polyalkyl (meth) acrylate rubber-like polymer (a1-2) 100 mass% It is preferable to contain 70 mass% or more of alkyl (meth) acrylate structural units, more preferable to contain 80 mass% or more, and further preferable to contain 90 mass% or more. When the content of the alkyl (meth) acrylate structural unit is 70% by mass or more, the impact resistance of the thermoplastic resin composition tends to be improved.

<Polyorganosiloxane rubber polymer (a1-3)>
The polyorganosiloxane rubber-like polymer (a1-3) is one or two selected from polyorganosiloxane (a1-3-1) or polyorganosiloxane composite rubber (a1-3-2) is necessary.

<Polyorganosiloxane (a1-3-1)>
The polyorganosiloxane (a1-3-1) is an organosiloxane, a grafting agent for polyorganosiloxane (hereinafter referred to as "siloxane crosslinking agent"), and, if necessary, a crosslinking agent for polyorganosiloxane (hereinafter referred to as "siloxane crosslinking" Obtained by emulsion polymerization of an organosiloxane mixture comprising an agent (hereinafter referred to as “agent”) and a siloxane oligomer having an end blocking group.

  As the organosiloxane, either a chain organosiloxane or a cyclic organosiloxane can be used, but a cyclic organosiloxane is preferable because it has high polymerization stability and high polymerization rate. The cyclic organosiloxane is preferably a three- or more-membered cyclic organosiloxane, and more preferably a three- to six-membered ring. Examples of cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclo Tetrasiloxane is mentioned. One of these may be used alone, or two or more may be used in combination.

  As a siloxane cross-linking agent, one capable of forming a bond with the organosiloxane via a siloxane bond and forming a bond with a monomer constituting the poly (meth) acrylic acid ester or a vinyl monomer such as a vinyl monomer preferable. Considering the reactivity with organosiloxanes, alkoxysilane compounds having a vinyl group are preferred. By using a siloxane crosslinking agent, it is possible to obtain a polyorganosiloxane having a functional group that can be polymerized with any vinyl copolymer. When the polyorganosiloxane has a functional group capable of polymerizing with any vinyl monomer, the polyorganosiloxane can be chemically bonded to the poly (meth) acrylic acid alkyl ester or vinyl monomer.

As a siloxane crossing agent, the siloxane represented by Formula (I) can be mentioned.
RSiR ¹ _n (OR ² ) _(3-n) Formula (I)
In formula (I), R ¹ represents a methyl group, an ethyl group, a propyl group or a phenyl group. R ² represents an organic group in the alkoxy group, and examples thereof include a methyl group, an ethyl group, a propyl group or a phenyl group. n is 0, 1 or 2; R represents any one of the groups represented by formulas (I-1) to (I-4).
^{_{CH 2 = C (R 3)}} -COO- (CH 2) p - formula (I-1)
CH ₂ = C (R ⁴ ) -C ₆ H ₄ -Formula (I-2)
CH ₂ = CH- formula (I-3)
HS-(CH ₂ ) _p -Formula (I-4)
In these formulas, R ³ and R ⁴ each represent hydrogen or a methyl group, and p represents an integer of 1 to 6.

  As a functional group represented by Formula (I-1), a methacryloyl oxyalkyl group can be mentioned. As the siloxane having this group, for example, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyl methoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxy Mention may be made of propylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane.

  As a functional group represented by Formula (I-2), a vinylphenyl group etc. can be mentioned. As a siloxane which has this group, vinylphenylethyl dimethoxysilane can be mentioned, for example.

  As a siloxane which has a functional group represented by Formula (I-3), vinyl trimethoxysilane and vinyl triethoxysilane can be mentioned, for example.

A mercapto alkyl group can be mentioned as a functional group represented by Formula (I-4). Examples of siloxanes having this group include γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropylmethoxydimethylsilane, γ-mercaptopropyldiethoxymethylsilane, γ-mercaptopropylethoxydimethylsilane, and γ-mercaptopropyltrimethoxysilane. be able to.
One of these siloxane crosslinking agents may be used alone, or two or more thereof may be used in combination.

  As a siloxane crosslinking agent, what has three or four functional groups which can be couple | bonded with the said organosiloxane is preferable. Examples of siloxane crosslinking agents include trialkoxyalkylsilanes such as trimethoxymethylsilane; trialkoxyarylsilanes such as triethoxyphenylsilane; tetramethoxysilane such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane and tetrabutoxysilane An alkoxysilane is mentioned. One of these may be used alone, or two or more may be used in combination. Among these, tetraalkoxysilane is preferable, and tetraethoxysilane is more preferable.

  The siloxane oligomer having a terminal blocking group refers to a siloxane oligomer having an alkyl group or the like at the end of the organosiloxane oligomer and stopping the polymerization of the polyorganosiloxane.

  As a siloxane oligomer having an end capping group, for example, hexamethyldisiloxane, 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane And methoxytrimethylsilane.

  The content of organosiloxane in the organosiloxane mixture (100% by mass) is preferably in the range of 60 to 99.9% by mass, and more preferably in the range of 70 to 99.9% by mass. The content of the siloxane crossing agent in the organosiloxane mixture (100% by mass) is preferably in the range of 0.1 to 10% by mass. The content of the siloxane crosslinking agent in the organosiloxane mixture (100% by mass) is preferably in the range of 0 to 30% by mass.

<Polyorganosiloxane composite rubber (C1-3-2)>
In the present invention, the polyorganosiloxane rubber (C1-3) contains a polyorganosiloxane (C1-3-1) and a vinyl polymer for composite rubber. It may be a polyorganosiloxane composite rubber (C1-3-2).
The vinyl polymer for composite rubber is obtained by polymerizing a vinyl monomer for composite rubber and, if necessary, a crosslinkable monomer or an acrylic crosslinking agent.

  Examples of the vinyl monomer for composite rubber include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and the like; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i -Alkyl methacrylates such as butyl methacrylate; aromatic vinyl monomers such as styrene and α-methylstyrene; and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. As the vinyl monomer for composite rubber, n-butyl acrylate is preferable because the impact resistance of the molded article is excellent.

  The crosslinkable monomer is a polyfunctional monomer having two or more polymerizable unsaturated bonds. For example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, diacrylic Examples thereof include acid 1,6-hexanediol and triallyl trimellitate, which may be used alone or in combination of two or more.

  The acrylic crosslinking agent is a polyfunctional monomer having two or more polymerizable unsaturated bonds having different reactivity. By having groups having different reactivities, when polymerized together with other components, unsaturated groups are incorporated into the composite rubber in a state of preserving them, which enables formation of a graft copolymer. For example, allyl methacrylate, triallyl cyanurate and triallyl isocyanurate can be mentioned, and these can be used alone or in combination of two or more. The acrylic crosslinking agent also has a function as a crosslinking agent since it has two or more polymerizable unsaturated bonds as in the case of the crosslinking monomer.

  0 to 15 parts are preferable and 0.1 to 10 parts of a crosslinkable monomer are preferable with respect to 100 mass parts of vinyl monomers for composite rubbers. When the amount of the crosslinkable monomer is 15 parts or less, the impact resistance of the molded article tends to be excellent.

  The amount of the acrylic crosslinking agent is preferably 0 to 15 parts, and more preferably 0.1 to 10 parts with respect to 100 parts by mass of the composite rubber vinyl monomer. When the amount of the crosslinkable monomer is 15 parts or less, the impact resistance of the molded article tends to be excellent.

  The content of polyorganosiloxane (a1-3-1) in 100% by mass of polyorganosiloxane composite rubber (a1-3-2) is preferably 0.1 to 99.9% by mass, and 5% by mass. % Or more is more preferable, and 7% by mass or more is particularly preferable. If the content of the polyorganosiloxane is 0.1% by mass or more, the impact resistance tends to be excellent. If the content of the polyorganosiloxane is 99.9% by mass or less, the heat resistance tends to be excellent.

<Method of producing rubbery polymer (a1)>
There are no particular limitations on the polymerization method for producing a rubber aqueous dispersion (an aqueous dispersion containing rubber particles) comprising a rubbery polymer (a1), but in aqueous systems, emulsion polymerization, suspension polymerization, solution polymerization, etc. in solution systems Can be mentioned. Emulsion polymerization is preferred in that the particle diameter control of the rubber particles and the rubber particles having a core-shell structure are easily obtained.

  As an emulsifier used for emulsion polymerization, a well-known anionic emulsifier, a cationic emulsifier, a nonionic emulsifier etc. can be used.

  The polymerization initiator used for the polymerization is not particularly limited, and for example, known azo initiators and peroxide initiators can be used. One of these may be used alone, or two or more may be used in combination. 0.05-1.0 mass part is preferable with respect to a total of 100 mass parts of a monomer, and, as for the usage-amount of a polymerization initiator, 0.1-0.3 mass part is more preferable.

  In the present invention, the proportion of the rubbery polymer (a1) in the core-shell type reinforcing agent aqueous dispersion (A1) can be set arbitrarily, but rubbery in 100% by mass of the core-shell type reinforcing agent It is preferable that a polymer (a1) is 50-90 mass%. If this value is 50% by mass or more, the impact resistance of the thermoplastic resin composition tends to be improved.

<Vinyl-based monomer (a2)>
Examples of the vinyl monomer (a2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i- Examples include butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, α-methylstyrene, vinyl toluene, chlorostyrene, acrylonitrile and methacrylonitrile. One of these may be used alone, or two or more may be used in combination. Acrylonitrile, methyl (meth) acrylate and styrene are preferable because they tend to be excellent in heat resistance of the thermoplastic resin composition.

  When a thermoplastic polyester resin is used as the thermoplastic resin (B), an epoxy group-containing vinyl monomer and, if necessary, another vinyl monomer copolymerizable to the vinyl monomer (a2) It is preferable to use the body.

  Examples of epoxy group-containing vinyl monomers include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, allyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, and polyalkylene. Glycidyl ether of glycol (meth) acrylate, glycidyl ester, etc. may be mentioned. Among these, glycidyl methacrylate is more preferable. These are used alone or in combination of two or more.

  Examples of the vinyl-based monomer copolymerizable with the epoxy group-containing vinyl-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n -Butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, α-methylstyrene, vinyl toluene, chlorostyrene, acrylonitrile, methacrylonitrile It can be mentioned. One of these may be used alone, or two or more may be used in combination.

<Method of Producing Core-Shell Type Reinforcing Agent Aqueous Dispersion (A1)>
The graft polymerization method of the vinyl monomer component to the rubbery polymer (a1) is not particularly limited, but emulsion polymerization is preferable because of the control of the particle diameter and the easy formation of the core-shell structure. As the emulsion polymerization method, generally known emulsion polymerization methods such as batch addition polymerization of monomers, continuous addition polymerization of monomers, multistage polymerization and the like can be employed. The addition of an emulsifying agent can also adopt the same method as the addition of a monomer. The graft layer may be a single layer or two or more layers.

<Polytetrafluoroethylene Aqueous Dispersion (A2)>
The polytetrafluoroethylene aqueous dispersion (A2) can be obtained by polymerizing a tetrafluoroethylene monomer by emulsion polymerization using a fluorine-containing surfactant.

  When emulsion polymerization of a polytetrafluoroethylene monomer is carried out, fluorine-containing olefin such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, perfluoroalkylvinylether or the like as a copolymer component as long as the characteristics of polytetrafluoroethylene are not impaired Fluorine-containing alkyl (meth) acrylates, such as perfluoroalkyl (meth) acrylate, can be used. The content of the copolymerization component is preferably 10% by mass or less based on tetrafluoroethylene.

  The polytetrafluoroethylene aqueous dispersion (A2) may be used in the form of an emulsion-polymerized aqueous dispersion, but it is preferably an aqueous dispersion concentrated by adding a dispersion stabilizer.

  Commercially available raw materials of the polytetrafluoroethylene aqueous dispersion (A2) include Fluon AD911E, AD915E, AD916E, AD939E manufactured by Asahi Glass Co., Ltd., polyflon PTFE D-210C manufactured by Daikin, Teflon 31 manufactured by DuPont Fluorochemicals, Ltd. As representative examples, JR, Shandong Higashidake DF 301, Shanghai 3F FR 301, FR 302 and the like can be mentioned.

<Method for recovering polytetrafluoroethylene-containing toughening agent (A)>
The polytetrafluoroethylene-containing toughener (A) of the present invention is prepared by mixing the core-shell toughener aqueous dispersion (A1) and the polytetrafluoroethylene aqueous dispersion (A2), spray recovering, or coagulating. It can be obtained by powder recovery.

  The polytetrafluoroethylene-containing toughening agent (A) may contain an aqueous dispersion (A3) obtained by emulsion polymerization of a vinyl monomer. As a method of adding an aqueous dispersion (A3) obtained by emulsion polymerization of a vinyl monomer, a core-shell type reinforcing agent aqueous dispersion (A1) and a polytetrafluoroethylene aqueous dispersion (A2) are used. Method of mixing and recovering by spraying, or coagulation and recovery, coagulation of composite aqueous dispersion obtained by mixing core-shell type reinforcing agent aqueous dispersion (A1) and polytetrafluoroethylene aqueous dispersion (A2) There is a method of adding an aqueous dispersion (A3) obtained by emulsion polymerization of a vinyl-based monomer.

<Thermoplastic resin (B)>
As a thermoplastic resin (B) which can be used for the thermoplastic resin composition of this invention, the following are mentioned, for example. Olefin resins such as polypropylene (PP) and polyethylene (PE); polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene -Maleic anhydride copolymer (SMA), acrylonitrile butadiene styrene copolymer (ABS), acrylic acid ester styrene styrene acrylonitrile copolymer (ASA), acrylonitrile ethylene propylene rubber styrene copolymer (AES) ) Styrene (St) based resins such as; Acrylic (Ac) based resins such as polymethyl methacrylate (PMMA); Polycarbonate based resins (PC based resins); Polyamide (PA) resins; Polyethylene terephthalate (PET); PEs resins such as phthalate (PBT) and polylactic acid (PLA); (modified) polyphenylene ether ((m-) PPE) resin, polyoxymethylene (POM) resin, polysulfone (PSO) resin, polyacrylate (PAr) Engineering plastics such as resin, polyphenylene (PPS) resin; thermoplastic polyurethane (PU) resin; alloy of PC resin such as PC / ABS etc. with St resin, PVC resin such as PVC / ABS etc and St resin Alloy, alloy of PA resin and St resin such as PA / ABS, alloy of PA resin and TPE, alloy of PA resin and St resin such as PA / ABS, alloy of PA resin and TPE, PA / PA Alloy of PA resin such as PP and polyolefin resin, alloy of PC resin such as PC / PBT and PEs resin, polio Alloys of olefin resins of fin resin / TPE and PP / PE, etc., alloys of PPE resin of PPE / HIPS, PPE / PBT and PPE / PA, etc. PVC resins such as PVC / PMMA and Ac Polymer alloy such as alloy with resin; PVC based resin such as hard vinyl chloride resin, semi-rigid vinyl chloride resin, soft vinyl chloride resin.

  It is preferable that the thermoplastic resin (B) contains, as a main component, at least one thermoplastic resin selected from polyester resins, polyamide resins, and polyarylene sulfide resins.

  Here, the polyester resin means terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, adipic acid as resin components. Ethylene glycol, propylene glycol, butanediol, pentane, and one or more kinds of dicarboxylic acids such as sebacic acid, azelaic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dimeric acid, or their ester-forming derivatives Diol, neopentyl glycol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-bis (4'-hydroxyethoxyphenyl) ester A polyester resin obtained by a polycondensation reaction from glycols selected from one or two or more of lopane, xylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, aliphatic polyester oligomer having hydroxyl groups at both ends It may be either homopolyester or copolyester. As comonomer components for constituting the copolyester, in addition to the above, there may be mentioned glycolic acid, hydroxy acid, hydroxybenzoic acid, hydroxyphenyl acid such as hydroxyphenylacetic acid and naphthyl glycolic acid, propiolactone, butyrolactone, caprolactone and valerolactone. Lactone compounds such as these can also be used, and polyfunctional ester forming components such as trimethylolpropane, trimethylolethane, pentaerythritol, trimellitic acid, trimesic acid and pyromellitic acid as long as thermoplasticity can be maintained. It may be a polyester having a branched or crosslinked structure using Also, aromatic nuclei such as ethylene or propionoxyside adducts of dibromoterephthalic acid, tetrabromoterephthalic acid, tetrachloroterephthalic acid, 1,4-dimethylol tetrabromobenzene, tetrabromobisphenol A, tetrabromobisphenol A Also included are polyester copolymers having a halogen compound using a compound having a halogen compound as a substituent and having an ester forming group. In addition, polyester-based elastomers constituting block copolymers of high melting point hard segment and low melting point soft segment can also be used. Examples of the polyester elastomer include block copolymers of a hard segment mainly composed of an alkylene terephthalate unit and a soft segment mainly composed of an aliphatic polyester or a polyether. These polyester resins may be used alone or in combination of two or more as the component (A). In addition, polylactic acid obtained by polymerizing lactic acid by ester bond can be used. Particularly preferable polyester resins are polybutylene terephthalate, polyethylene terephthalate and copolymers having these as main repeating units, and as a comonomer component forming the copolymer, isophthalic acid, bisphenol A, 2, 2 is particularly preferable. And -bis (β-hydroxyethoxyphenyl) propane, 2,2-bis (β-hydroxyethoxytetrabromophenyl) propane and the like.

The polyamide resin is not particularly limited, and means an amino acid lactam, or a general melt polymerizable and melt formable polymer composed of a diamine and a dicarboxylic acid. Specific examples of the polyamide resin used in the present invention include the following resins. (1) Polycondensate of an organic dicarboxylic acid having 4 to 12 carbon atoms and an organic diamine having 2 to 13 carbon atoms, such as polyhexamethylene adipamide which is a polycondensate of hexamethylene diamine and adipic acid [6, 6 nylon], polyhexamethylene azelamide [6, 9 nylon] which is a polycondensate of hexamethylene diamine and azelaic acid, polyhexamethylene sebaca which is a polycondensate of hexamethylene diamine and sebacic acid Midori [6, 10 nylon], polyhexamethylene dodecanoamide [6, 12 nylon] which is a polycondensate of hexamethylenediamine and dodecanedioic acid, polycondensation of bis-p-aminocyclohexylmethane with dodecanedioic acid Polybis (4-aminocyclohexyl) methododecane, (2) the weight of ω-amino acid Condensate such as polyundecanamide [11 nylon] which is polycondensate of ω-aminoundecanoic acid, (3) ring-opening polymer of lactam, for example poly coupleromid [6 nylon] which is ring-opening polymer of ε-aminocaprolactam And a ring-opened polymer of ε-amino laurolactam such as polylauric lactam [12 nylon]. Among them, polyhexamethylene adipamide (6, 6 nylon), polyhexamethylene azelamide (6, 9 nylon) and polycaprolamide (6 nylon) are preferably used.
Further, in the present invention, for example, a polyamide resin produced from adipic acid, isophthalic acid and hexamethylene diamine can also be used, and two or more kinds such as a mixture of 6 nylon and 6, 6 nylon can be used. It is also possible to use a blend compounded with a polyamide resin of

  The polyamide resin (1) can be prepared, for example, by polycondensation of equimolar amounts of an organic dicarboxylic acid having 4 to 12 carbon atoms and an organic diamine having 2 to 13 carbon atoms. Also, if necessary, an organic dicarboxylic acid can be used in a larger amount than an organic diamine so that the carboxy group in the polyamide resin is in excess of the amino group, or conversely, the amino group in the polyamide resin is carboxy Organic dicarboxylic acids can also be used in smaller amounts than organic diamines in excess of the groups.

  Specific examples of the organic dicarboxylic acid include adipic acid, pimelic acid, suberic acid, sebacic acid and dodecanedioic acid. Specifically as said organic diamine, hexamethylene diamine, octamethylene diamine, etc. are mentioned.

  Further, the polyamide resin of the above (1) may also be prepared from a derivative capable of producing a carboxylic acid such as an ester or an acid chloride and a derivative capable of producing an amine such as an amine salt in the same manner as the above method. it can.

  The polyamide resin of the above (2) can be prepared, for example, by polycondensation by heating an ω-amino acid in the presence of a small amount of water. In most cases, a small amount of a viscosity stabilizer such as acetic acid is added.

  The polyamide resin of the above (3) can be prepared, for example, by ring-opening polymerization of a lactam by heating in the presence of a small amount of water. In most cases, a small amount of a viscosity stabilizer such as acetic acid is added.

The polyarylene sulfide resin that can be used in the present invention is a repeating unit represented by the general formula-(Ar-S)-[wherein Ar is represented by the following formula,
(X represents -SO _2- , -CO-, -O-, or an alkylene group having 1 to 5 carbon atoms which may have a lower alkyl side chain.)
And at least one selected from those having one to eight substituents such as a halogen or a methyl group in these aromatic rings. ] May be a polymer having only a linear structure, and may have a crosslinked structure as long as it has melt processability.

  The present invention is further described in detail by the following examples and comparative examples. "Part" in the description indicates "mass part".

Production Example 1 Production of Acrylic Rubber Impact Strength Modifier (A-1) 99 parts of 2-ethylhexyl acrylate and 1 part of allyl methacrylate were mixed to obtain 100 parts of a (meth) acrylate monomer mixture. 100 parts of the above (meth) acrylate monomer mixture is added to 300 parts of distilled water in which 1 part of alkenyl oxalic acid dipotassium salt is dissolved, and after preliminary stirring at 10,000 rpm with a homomixer, pressure of 300 kg / cm ^{2 with} a homogenizer The mixture was emulsified and dispersed to obtain a (meth) acrylate emulsion. This mixture is transferred to a separable flask equipped with a condenser and stirring blades, heated at 70 ° C. with nitrogen displacement and mixing, and 1 part of potassium persulfate dissolved in a small amount of water is added at 70 ° C. It was left to stand for 5 hours, and the polymerization was completed to obtain a latex (ALx-1) of an acrylic rubber (A-1).

  The polymerization rate of the obtained latex (ALx-1) of acrylic rubber (A-1) was 98.5%, and the average particle size was 0.19 μm. The latex was coagulated and dried with ethanol to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 91.4% by mass.

  120 parts of the latex (ALx-1) of the above acrylic rubber (A-1) is collected, put into a separable flask equipped with a stirrer, added with 205 parts of distilled water, purged with nitrogen and heated to 50 ° C. A mixed solution of 53.9 parts of n-butyl acrylate which is a component of acrylic rubber (B-1), 1.1 parts of allyl methacrylate and 0.22 parts of tert-butyl hydroperoxide is added and stirred for 30 minutes, and this mixture is added. The liquid was allowed to penetrate into latex (ALx-1) particles of acrylic rubber (A-1). Next, a mixed solution of 0.002 parts of ferrous sulfate, 0.006 parts of ethylenediaminetetraacetic acid disodium salt, 0.26 parts of Rongalite and 5 parts of distilled water is charged to start radical polymerization, and then an internal temperature of 70 ° C. The polymerization was completed by holding for a time to obtain a latex (ABLx-1) of a polyalkyl (meth) acrylate rubber (AB-1). A part of this latex was collected, and the average particle size of the polyalkyl (meth) acrylate rubber was measured, which was 0.24 μm. Further, this latex was dried to obtain a solid, which was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 97.3% by mass.

  To this polyalkyl (meth) acrylate rubber latex, a mixture of 0.06 part of tert-butyl hydroperoxide and 15 parts of methyl methacrylate is added dropwise at 70 ° C. for 15 minutes, and then kept at 70 ° C. for 4 hours, The graft polymerization on the polyalkyl (meth) acrylate rubber was completed. The conversion of methyl methacrylate was 96.4%. The obtained graft copolymer latex is dropped into 200 parts of hot water of 8% by mass of calcium acetate, coagulated, separated and washed, then dried at 75 ° C. for 16 hours, and a powdery acrylic rubber impact strength modifier 98.9 parts of (A-1) were obtained.

Production Example 2 Production of Acrylic Rubber Impact Strength Modifier (A-2) Polyalkyl (meth) acrylate rubber latex (ABLx-1): Monomer component: 12 parts of methyl methacrylate, 3 parts of glycidyl methacrylate A powdery acrylic rubber-based impact strength modifier (A-2) was obtained 98.8 parts in the same manner as in Production Example 1 except for the above.

Production Example 3 Production of Acrylic Rubber Impact Strength Modifier (A-3) The graft copolymer latex obtained in Production Example 2 and an aqueous dispersion of polytetrafluoroethylene made by Asahi Glass Co. (Fluon AD939E) 3.33 A powdery acrylic rubber impact strength modifier (A-3) was obtained in an amount of 100.9 parts in the same manner as in Production Example 2 except that parts were stirred and mixed.

Abbreviations of compounds used in the following Examples and Comparative Examples are shown below.
PBT: Mitsubishi Engineering Plastics Corporation Nova Duran 5010R5
A-3000: Metabrene A-3000 (Mitsubishi Chemical Corporation, special acrylic modified PTFE)
CD-1: Fluon CD123 E (manufactured by Asahi Glass Co., Ltd., PTFE fine powder)

(Method of preparing pellet and test piece)
Screws were mixed using the PBT and acrylic rubber impact strength modifiers in the formulations shown in Table 1 and heated to a barrel temperature of 260 ° C. using a devolatilizing extruder (Ikegai Co., Ltd., trade name: PCM-30) It knead | mixed on conditions of rotation speed 150 rpm, and obtained the pellet-form polybutylene-terephthalate-resin composition.
The obtained pellet-like polybutylene terephthalate resin composition is dried at 120 ° C. for 6 hours using a hot air drier and then 100 t injection molding machine (trade name: SE-100DU, manufactured by Sumitomo Heavy Industries, Ltd.) Then, molding was performed under conditions of a cylinder temperature of 260 ° C. and a mold temperature of 70 ° C. to obtain an ISO dumbbell test piece 1 and a test piece 2 (length 80 mm, width 10 mm, thickness 4 mm).

(Evaluation of impact resistance)
Notched Charpy impact strength was measured using the test piece 2 at measurement temperatures of 23 ° C. and −30 ° C. according to JIS K7111.

(Measurement of flexural modulus and maximum bending strength)
Using the test piece 1, the bending yield strength was measured at a measurement temperature of 23 ° C. according to JIS K7171.

  From the results of Table 1, from the polybutylene terephthalate resin composition of each Example, a molded article (test piece) having excellent impact resistance and high bending yield point strength was obtained.

Claims (4)

  A polytetrafluoroethylene-containing reinforcing agent (A) obtained by mixing the core-shell reinforcing agent aqueous dispersion (A1) and the polytetrafluoroethylene aqueous dispersion (A2) and recovering the powder.   A thermoplastic resin composition comprising the polytetrafluoroethylene-containing toughening agent (A) according to claim 1 and a thermoplastic resin (B).   The thermoplastic resin composition according to claim 2, wherein the thermoplastic resin (B) is a polyester resin.   The thermoplastic resin composition according to claim 3, wherein the polyester resin (B) is a polybutylene terephthalate resin.