JP2011111468A - Resin composition, molded product thereof and container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide-based resin composition for providing a molded product having excellent mechanical strength and chemical resistance and a molded product thereof. <P>SOLUTION: The resin composition is a polyphenylene sulfide-based resin composition comprising 100 pts.wt. of a polyphenylene sulfide-based resin and 5-50 pts.wt. of a siloxane rubber polymer-containing multilayer-structured polymer in which 100 wt.% of the siloxane rubber polymer-containing multilayer-structured polymer comprises a rubber core layer composed of 60-90 wt.% of a siloxane rubber polymer (A), a hard intermediate layer that covers the rubber core layer and is composed of 0.1-10 wt.% of a polyfunctional monomer-based polymer (B) and a shell layer that covers the hard intermediate layer and is composed of 4.9-34.9 wt.% of an ethylenic unsaturated monomer-based polymer (C) and 5-30 wt.% of an epoxy group-containing monomer-based polymer (D). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition, a molded body thereof, and a container.

  With respect to polyphenylene sulfide resin (PPS resin), several studies have been made so far for the purpose of improving impact resistance.

  For example, Patent Documents 1 and 2 disclose a composition in which an olefin copolymer composed of an unsaturated acid glycidyl ester is blended with a PPS resin. Patent Document 3 discloses a composition having a phase structure composed of a polyolefin resin and a PPS resin, the PPS resin being a matrix resin, and the polyolefin resin being a dispersion layer. However, the specifically disclosed composition has insufficient mechanical strength and chemical resistance.

  Patent Document 4 contains 1 to 100 parts by weight of a modified polyolefin obtained by extrusion modification by adding a reactive functional group-containing monomer such as glycidyl methacrylate / maleic anhydride to a polyolefin with respect to 100 parts by weight of a PPS resin. A PPS composition is disclosed. However, since the component that gives strength is polyolefin, the mechanical strength at low temperature cannot be said to be sufficient, and it is difficult to say that the chemical resistance is sufficient.

  Further, Patent Document 5 discloses a polyphenylene sulfide resin composition containing 0.05 to 10 parts by weight of a polyolefin having a carboxylic acid anhydride content of 10% by weight or more with respect to 100 parts by weight of the polyphenylene sulfide resin. . However, the purpose is to reduce burrs during injection molding, and it cannot be said that the mechanical strength and chemical resistance are sufficient.

Japanese Patent Publication No. 2-382 JP-A-5-239363 JP 2001-302917 A JP 2000-265059 A JP-A-11-269385

  An object of the present invention is to provide a polyphenylene sulfide-based resin composition from which a molded article excellent in mechanical strength and chemical resistance can be obtained, and a molded article thereof.

  As a result of intensive studies, the present inventor has found that a molded article having excellent mechanical strength and chemical resistance can be obtained by using a polyphenylene sulfide-based resin composition having a specific configuration, and has completed the present invention.

That is, the present invention is a polyphenylene sulfide resin composition comprising 100 parts by weight of a polyphenylene sulfide resin and 5 to 50 parts by weight of a siloxane rubber polymer-containing multilayer structure polymer,
100% by weight of the siloxane rubber polymer-containing multilayer structure polymer is a rubber core layer comprising 60 to 90% by weight of the siloxane rubber polymer (A); and the polyfunctional monomer-based polymer (B) 0 covering the rubber core layer A hard intermediate layer composed of 0.1 to 10% by weight; and 4.9 to 34.9% by weight of an ethylenically unsaturated monomer polymer (C) covering the hard intermediate layer, and an epoxy group-containing monomer polymer ( D) It relates to a polyphenylene sulfide resin composition comprising a shell layer comprising 5 to 30% by weight.

  In a preferred embodiment, the shell layer comprises a reactive shell layer composed of 5 to 20% by weight of the epoxy group-containing monomer polymer (D), and the ethylenically unsaturated monomer polymer (C). The reactive control shell layer consists of 9% to 34.9% by weight.

  A preferred embodiment is that the polyphenylene sulfide resin is a polyphenylene sulfide resin.

  Moreover, this invention relates to the molded object formed by shape | molding such a polyphenylene sulfide type-resin composition of this invention.

  Such a molded article of the present invention is suitable as a container for liquid organic matter.

  The resin composition of this invention turns into a resin composition from which the molded object which is excellent in mechanical strength and chemical resistance is obtained.

(Polyphenylene sulfide resin composition)
The resin composition of the present invention is a polyphenylene sulfide resin composition containing 100 parts by weight of a polyphenylene sulfide resin and 5 to 50 parts by weight of a siloxane rubber polymer-containing multilayer structure polymer, and the molded product has strength and chemical resistance. Excellent balance of sex.

  The polyphenylene sulfide resin composition of the present invention is required to contain 5 to 50 parts by weight of the siloxane rubber polymer-containing multilayer structure polymer with respect to 100 parts by weight of the polyphenylene sulfide resin. From the viewpoint of characteristics and moldability, it is preferable to contain 10 to 40 parts by weight or more.

(Mixing method)
Mixing of the components of the resin composition of the present invention can be performed by a known kneading machine. Examples of such a kneading machine include a mixing roll, a calender roll, a Banbury mixer, a Henschel mixer, a ribbon blender, a kneader, an extruder, a blow molding machine, and an inflation molding machine.

(Polyphenylene sulfide resin)
100% by weight of the polyphenylene sulfide resin according to the present invention is a thermoplastic resin containing as a main component a so-called polyphenylene sulfide resin containing 50% by weight or more of polyphenylene sulfide resin and less than 50% by weight of other thermoplastic resins. From the viewpoint of chemical properties, it is more preferable to use 100% by weight of polyphenylene sulfide resin.

(Polyphenylene sulfide resin)
The polyphenylene sulfide resin (PPS resin) according to the present invention is a polymer having a degree of polymerization of 80 to 300 having a repeating unit represented by the following general formula 1 of 50 mol% or more, preferably 70 mol% or more. Although the unit shown in the following general formula group 2 is mentioned, these copolymer components are preferably 10 mol% or less.

  To such PPS resin, molecular weight is improved by adding a cross-linking mold for injection molding that is cross-linked by heat treatment in the presence of oxygen to increase the melt viscosity, and lithium chloride, organic acid salt, water, etc. in the polymerization system. Although there is a linear type for injection molding, fiber, and film, a linear type that is more excellent in elongation and toughness than a crosslinked type is preferable from the viewpoint of sufficiently obtaining the effects of the present invention.

(Wherein R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal salt thereof)

(Other thermoplastic resins)
Examples of the other thermoplastic resins include polycarbonate resins such as aromatic polycarbonate and aliphatic polycarbonate, polyester carbonate resins, polyphenylene ether resins, polysulfone-based resins, polyether sulfone resins, polyarylene resins, polyamide resins such as nylon, poly Ether imide resins, polyacetal resins such as polyoxymethylene, polyvinyl acetal resins, polyketone resins, polyether ketone resins, polyether ether ketone resins, polyaryl ketone resins, polyether nitrile resins, liquid crystal resins, polybenzimidazole resins, polyparabanic acids Group consisting of resin, diene compound, maleimide compound, aromatic alkenyl compound, methacrylic acid ester, acrylic acid ester, and vinyl cyanide compound Ri 1 or more vinyl obtain a vinyl monomer polymerization or by copolymerizing a polymer or copolymer resin selected, polyolefin resins, and vinyl chloride resin. These can be used alone or in a blend of two or more. From the viewpoint of mechanical properties, chemical resistance, and cost, polyolefin resins, particularly polyethylene, are particularly preferable.

(Siloxane rubber polymer-containing multilayer structure polymer)
The siloxane rubber polymer-containing multilayer structure polymer according to the present invention comprises a rubber core layer comprising a siloxane rubber polymer (A), at least a unit derived from a polyfunctional monomer having two or more radical polymerizable groups in the molecule. Hard intermediate layer comprising polyfunctional monomer-based polymer (B) having, ethylenically unsaturated monomer polymer (C) derived from ethylenically unsaturated monomer, and epoxy group derived from epoxy group-containing monomer A composition comprising as a main component a multi-layer structure polymer including at least three layers of a shell layer comprising a monomer polymer containing (D). Basically, the rubber core layer comprising (A), the rubber core layer comprising Multilayer structure polymer having a so-called core shell (CSR) structure comprising a hard intermediate layer comprising a cover (B), a shell layer comprising the hard intermediate layer (C) and (D), ie, rubber Containing multilayer It is a concrete polymer (CSR). This CSR, and so-called free polymers composed of (B), (C), (D), etc., which are not grafted on (A) may be used as constituents of the composition, and are preferably composed of only CSR. Yes.

  Such a siloxane rubber polymer-containing multilayer structure polymer is obtained by, for example, polymerizing a monomer containing a polyfunctional monomer as a main component in the presence of the siloxane rubber polymer (A). (B) is obtained, and further, an ethylenically unsaturated monomer polymer (C) and an epoxy group are obtained by polymerizing an ethylenically unsaturated monomer and a monomer for shell layer comprising an epoxy group-containing monomer. It can produce by obtaining a containing monomer polymer (D).

  Such a siloxane rubber polymer-containing multilayer structure polymer has a volume average particle diameter of 0.008 from the viewpoint of stably obtaining particles and sufficient flame retardancy and impact resistance of the final molded product. ˜0.6 μm is preferable, 0.01 to 0.35 μm is more preferable, and 0.20 to 0.35 μm is particularly preferable.

  Such a siloxane rubber polymer-containing multilayer structure polymer is preferably obtained as an aqueous latex after the above polymerization, and this aqueous latex has a divalent or higher metal salt such as calcium chloride, magnesium chloride, magnesium sulfate, aluminum chloride. It is usually produced as a powder by a coagulation method in which it is solidified by adding heat treatment, dehydration, washing, drying and then recovered as a powder, or a spray drying method in which this aqueous latex is spray-dried and directly recovered as a powder. The Further, in the middle of the step of obtaining the siloxane rubber polymer-containing multilayer structure polymer powder according to the present invention in this way, more preferably by adding several water washing steps, the powder was used at the time of polymerization. Reduces metal impurities having catalytic decomposition action on PC such as organic sodium salt and organic potassium salt derived from auxiliary materials such as emulsifier, dispersant, pH adjuster, polymerization initiation assistant, etc., for example, the total amount of these is 10 ppm The following is preferable because the resin composition of the present invention has higher quality. Further, the aqueous latex is mixed with an organic solvent having a solubility in water at 20 ° C. of 5% by mass or more and 40% by mass or less, and further mixed with excess water to obtain a siloxane rubber polymer-containing multilayer structure polymer. There is a method of recovering by a water coagulation method in which a slow agglomerate of this polymer is obtained by slow agglomeration and then separated and recovered from the liquid phase and recovered as a powder by dehydration and drying.

  The epoxy group-containing monomer polymer (D) is stably dispersed in the matrix structure of the siloxane rubber polymer-containing multilayer structure polymer according to the present invention by reacting with a polyphenylene sulfide resin that is a matrix resin. Since the function is fulfilled, it is important that the epoxy group maintains the activity in the state of the siloxane rubber polymer-containing multilayer structure polymer recovered as a powder as described above. On the other hand, since the epoxy group maintains its activity, the multi-layered polymers are firmly bonded to each other, making it difficult to recover as a powder or difficult to disperse as primary particles in the matrix. There's a problem.

  In order to cope with such a problem, when the solidification method is used, the shell layer includes a reactive shell layer made of the epoxy group-containing monomer polymer (D) covering the hard intermediate layer, and the reactivity. As two layers of the reactive control shell layer made of the ethylenically unsaturated monomer polymer (C) covering the shell layer, it is preferable to prevent deactivation of the epoxy group in the solidification heat treatment step.

  Further, when the spray drying method or the water coagulation method is used, the reactive control shell layer is not polymerized among the shell layers, or the reactive shell layer and the reactive control shell layer are polymerized. It is also preferable to reverse the order.

  When such a siloxane rubber polymer-containing multilayer structure polymer powder is blended into a matrix resin to obtain a resin composition, if the matrix resin is a powder, the powder The volume average particle diameter is preferably 1 μm or more, more preferably 10 μm or more, further 50 μm or more, preferably 1 mm or less, more preferably 500 μm or less, and further preferably 200 μm or less. In particular, it is preferable that the average particle diameter of the matrix resin powder is close to or similar to the volume average particle diameter because classification is difficult. The powder is preferably in a state in which the copolymer of the present invention is gently agglomerated because it is easily dispersed in the state of primary particles of the multilayer structure polymer in the matrix resin.

  The siloxane rubber polymer-containing multilayer structure polymer according to the present invention is 100% by weight, and the siloxane rubber polymer (A) is contained in an amount of 60% by weight or more so as not to impair the mechanical properties of the resin composition according to the present invention. It is preferable to contain 65% by weight or more. The upper limit is 90% by weight in order to improve the dispersion state of the siloxane rubber polymer (A) component in the matrix resin.

  The polymer (B) having at least a unit derived from a polyfunctional monomer having two or more radical polymerizable groups in the molecule, where the siloxane rubber polymer-containing multilayer structure polymer according to the present invention is 100% by weight. In order not to impair the flame retardancy of the resin composition according to the present invention, it is preferably contained in an amount of 0.1% by weight or more, more preferably 0.5% by weight or more, and further preferably 1% by weight or more. Preferably, it is 10 wt% or less, more preferably 1 to 5 wt%. This ratio is a single unit for forming the polymer (B) with respect to the siloxane rubber polymer-containing multilayer structure polymer according to the present invention. It is a value that is considered to be the same as the weight of the mer.

  100% by weight of the siloxane rubber polymer-containing multilayer structure polymer according to the present invention, the polymer (C) derived from the ethylenically unsaturated monomer does not impair the flame retardancy of the resin composition according to the present invention. Therefore, in order to ensure compatibility between the siloxane rubber polymer-containing multilayer structure polymer according to the present invention and the matrix resin, it is preferably contained in an amount of 0.5% by weight or more, more preferably 3% by weight or more, further 5% by weight or more, preferably 34.9% by weight or less, more preferably 24.5% by weight or less, and further preferably 15% by weight or less. It is the value considered that it is the same as the weight of the said ethylenically unsaturated monomer with respect to the siloxane rubber polymer containing multilayer structure polymer which concerns on this.

(Siloxane rubber polymer (A))
The siloxane rubber polymer (A) is a component for improving impact resistance particularly at low temperatures without reducing flame retardancy, and in some cases improves flame retardancy of a resin composition containing itself. It is a component to be made. In the siloxane rubber polymer (A), siloxane rubber polymers such as polydimethylsiloxane, polymethylphenylsiloxane, polydimethylsiloxane-diphenylsiloxane copolymer, etc., and a part of side chain alkyl groups are substituted with hydrogen atoms. Polyorganohydrogensiloxane and the like can be used. Of these, polydimethylsiloxane, polymethylphenylsiloxane, and polydimethylsiloxane-diphenylsiloxane copolymer are preferable for imparting flame retardancy, and polydimethylsiloxane is most preferable because it is easily available economically.

  The weight average molecular weight of the siloxane rubber polymer (A) is preferably 100,000 or more from the viewpoint of ensuring the flame retardancy and impact resistance of the final molded body and ensuring the productivity. Preferably it is 150,000 or more, Preferably it is 1,000,000 or less, More preferably, it is 700,000 or less, Furthermore, it is 300,000 or less. The weight average molecular weight may be a standard polystyrene equivalent value determined by gel permeation chromatography (GPC) analysis.

  Specifically, the siloxane rubber polymer (A) is dimethyldichlorosilane, dimethyldialkoxysilane, cyclic siloxane represented by 1,3,5,7-octamethylcyclotetrasiloxane (D4), preferably weight. The raw material for forming the siloxane rubber polymer (A) mainly composed of a linear or branched organosiloxane oligomer having an average molecular weight of 500 to 20,000 or less, such as acid, alkali, salt, fluorine compound, etc. Preferable examples include siloxane rubber polymers polymerized by a method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method using a catalyst. When the linear or branched organosiloxane oligomer in which the residual volatile low molecular weight cyclic siloxane is reduced in advance is used as a raw material for the siloxane rubber polymer (A), the formed siloxane rubber polymer Residual volatile low molecular weight cyclic siloxane in (A) can be reduced, and steps such as stripping can be omitted.

  Further, in 100% by weight of the monomer for forming the siloxane rubber polymer (A), from the viewpoint of sufficiently maintaining rubber elasticity and forming a cross-linked structure, methyltriethoxysilane, tetrapropyl, as necessary. One or more selected from the group consisting of a trifunctional or higher functional alkoxysilane such as oxysilane and a trifunctional or higher functional silane condensate such as methyl orthosilicate may be contained in an amount of 0.1 wt% to 10 wt%.

  Further, in 100% by weight of the raw material for forming the siloxane rubber polymer (A), a radical polymerizable group is introduced into the siloxane rubber polymer (A), whereby the siloxane rubber of the hard intermediate layer according to the present invention is used. From the viewpoint of facilitating coating on the polymer (A), hydrolyzability of mercaptopropyldimethoxymethylsilane, acryloyloxypropyldimethoxymethylsilane, methacryloyloxypropyldimethoxymethylsilane, vinyldimethoxymethylsilane, vinylphenyldimethoxymethylsilane, etc. It is preferable that 0.1% by weight to 10% by weight of a graft crossing agent which is a silane compound containing a group and a radical polymerizable group is contained.

  A silane compound that is a tri- or higher functional alkoxysilane such as methacryloyloxypropyltrimethoxysilane and has a radically polymerizable group can also be used.

  In order to satisfactorily develop the impact resistance of the final molded body, the siloxane rubber polymer (A) is preferably particles. Such particles can be produced from organosiloxanes as described above by emulsion polymerization. Instead of the emulsion polymerization method, a modified or non-modified siloxane rubber polymer (A) obtained by modifying an emulsion siloxane rubber polymer, solution polymerization method or the like is mechanically forcedly emulsified using a high-pressure homogenizer. An emulsion of the siloxane rubber polymer (A) can be obtained by a method such as

Thus, when the siloxane rubber polymer (A) is a particle, from the viewpoint of stably obtaining the particle, and from the viewpoint of sufficient flame retardancy and impact resistance of the final molded body, the volume average particle thereof The diameter is preferably 0.008 to 0.6 [mu] m, more preferably 0.01 to 0.35 [mu] m, particularly preferably 0.17 to 0.32 [mu] m, and thus particles of the siloxane rubber polymer (A). per rubber particles, the number average area occupied by the particles of the resin composition or its molded article of the present invention is measured by observing an electron microscope photograph or the like, and more preferably 0.01~0.12μm ^2. The volume average particle diameter can be measured using, for example, MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd.

  Here, when polymerizing the siloxane rubber polymer (A), a seed polymerization method can be applied. For example, a method using an organic polymer such as polybutyl acrylate as a seed particle, a method using a siloxane rubber polymer latex as a seed latex, and the like can be preferably exemplified. In this case, the latex particle diameter of the seed particle is 30 nm or less. Preferably, it is 25 nm or less, more preferably 10 nm or less, 1 nm or more, more preferably 5 nm or more.

  The modified or non-modified (poly) organosiloxane, preferably having reduced residual volatile low molecular weight cyclic siloxane in advance, is added with water, a surfactant, etc., if necessary, together with the graft crossing agent, etc. After primary mixing with a line mixer or circulation pump, etc., it is mechanically emulsified with a high-pressure homogenizer or colloidal mill to obtain the desired particle size, and an acid such as dodecylbenzenesulfonic acid is added to at least 0 ° C., preferably 100 ° C. Thereafter, it can be produced by further polymerizing at 30 ° C. or lower, particularly 25 ° C. or lower, further reacting with a graft crossing agent or the like as necessary, and then neutralizing.

  When acidic polymerization conditions are used in the polymerization of the cyclic siloxane or the like or the forced emulsion polymerization of (poly) organosiloxane or the like, a surfactant that exhibits surface activity even under acidic conditions may be used. preferable. Examples of such surfactants include anionic surfactants such as metal salts of alkyl sulfates, metal salts of alkyl sulfonic acids, and metal salts of alkyl aryl sulfonic acids. The metal salt is preferably an alkali metal salt, particularly a sodium salt or potassium salt. Of these, sodium salts are preferable, and sodium dodecylbenzenesulfonate is most preferable. In addition, polyoxyalkylene alkyl ether typified by polyoxyethylene dodecyl ether, polyoxyalkylene alkyl aryl ether typified by polyoxyethylene nonylphenyl ether, polyoxyalkylene higher fatty acid ester typified by polyoxyethylene stearate ester Nonionic surfactants such as sorbitan monolaurate can be used. Alternatively, they can be used in combination with the anionic surfactant.

(Polyfunctional monomer polymer (B))
The polymer (B) having at least a unit derived from a nitrogen atom-containing polyfunctional monomer having two or more radically polymerizable groups in the molecule includes the polymer (C) of the ethylenically unsaturated monomer. The siloxane rubber polymer (A) can be grafted onto the siloxane rubber polymer (A), thereby reducing the amount of the ethylenically unsaturated monomer used. The ratio of the siloxane rubber polymer (A) component in the coalescence-containing multilayer structure polymer can be increased. As a result, the amount of the ethylenically unsaturated monomer that is a combustible component can be reduced, and deterioration of the flame retardancy of the resulting resin composition can be suppressed or improved. When the polymer derived from a nitrogen atom-containing polyfunctional monomer is used as the polyfunctional monomer-derived polymer (B), further improve the heat resistance of the siloxane rubber polymer-based copolymer itself. Can do. This is considered to be due to the high heat resistance of the polymer (B) derived from the nitrogen atom-containing polyfunctional monomer. Compared with the case of using a polymer having at least units derived from methacrylate-based polyfunctional monomers such as allyl methacrylate and 1,3 monobutylene glycol dimethacrylate, dienes such as butadiene, and divinylbenzene. The deterioration of flame retardancy can be suppressed or improved.

  The polymer (B) having at least a unit derived from a nitrogen atom-containing polyfunctional monomer having two or more radically polymerizable groups in the molecule includes a nitrogen atom-containing polyfunctional monomer described later, This is a polymer obtained by polymerizing a polymer (B) -forming monomer, which is a mixture of the above-mentioned other monomers copolymerizable with this, using a known radical polymerization method. When the siloxane rubber polymer (A) is obtained as an emulsion, the polymer (B) is preferably obtained by an emulsion polymerization method. In this case, a known polymerization initiator, that is, 2,2′- It can be used as a thermal decomposition type polymerization initiator such as azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate. In addition, since the polymerization temperature can be set in a wide range including a relatively low temperature, t-butyl peroxyisopropyl carbonate, paramentane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t Organic peroxides such as monobutyl peroxide, t-hexyl peroxide, peroxides such as inorganic peroxides such as hydrogen peroxide, potassium persulfate and ammonium persulfate, and sodium formaldehyde sulfoxylate and glucose as necessary Are preferably used in combination as a redox-type polymerization initiator. In this case, if necessary, a transition metal salt such as iron (II) sulfate, and if necessary, a chelating agent such as disodium ethylenediaminetetraacetate , If necessary It is preferable to use a phosphorus-containing compounds such as sodium pyrophosphate Te. Among the organic peroxide hydrogen peroxides, it is preferable to use an aromatic ring-containing peroxide such as cumene hydroperoxide or dicumyl peroxide as a redox polymerization initiator.

  The proportion of the nitrogen atom-containing polyfunctional monomer in 100% by weight of the polymer (B) -forming monomer is preferably 20% by weight or more, and 50% by weight from the viewpoint of flame retardancy according to the present invention. The above is more preferable, 80% by weight or more is further preferable, and 100% by weight is most preferable.

  Examples of the nitrogen atom-containing polyfunctional monomer include tertiary amines such as triallylamine, diallyl isocyanurate, diallyl-n-propyl isocyanurate, triallyl isocyanurate, trimethallyl isocyanurate, tris ((meth) acryloxy). Examples thereof include compounds having an isocyanuric acid skeleton such as ethyl) isocyanurate, compounds having a cyanuric acid skeleton represented by triallyl cyanurate, tri (meth) acryloylhexahydrotriazine, etc., among which compounds having an isocyanuric acid skeleton, particularly Triallyl isocyanurate or a compound having a cyanuric acid skeleton, particularly triallyl cyanurate is preferred, and triallyl isocyanurate is most preferred.

  As the other monomer copolymerizable with the nitrogen atom-containing polyfunctional monomer, those similar to the ethylenically unsaturated monomer described later can be used. In addition, divinylbenzene, divinylnaphthalene, divinyl are used. Anthracene, diisopropenylbenzene, allyl (meth) acrylate, triallylbenzene tricarboxylate, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 2,2′-divinylbiphenyl, 2,4′- Divinylbiphenyl, 3,3L divinylbiphenyl, 4,4L divinylbiphenyl, 2,4'-di (2 monopropenyl) biphenyl, 4,4L di (2 monopropenyl) biphenyl, 2,2'-divinyl-4 monoethyl-4 ' -Propylbiphenyl, 3,5,4L trivinyl bif Polyfunctional monomers such as sulfonyl may also be employed. In addition, as other monomers copolymerizable with the nitrogen atom-containing polyfunctional monomer, aromatic compounds such as styrene, α-methyl styrene, vinyl naphthalene, vinyl biphenyl, etc. are used for the expression of good flame retardancy. Vinyl monomers, vinyl cyanide monomers such as acrylonitrile, alkyl (meth) acrylates having an alkyl group of 2 or less, such as methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate, 2,2′-divinyl Biphenyl, 2,4′-divinylbiphenyl, 3,3L divinylbiphenyl, 4,4L divinylbiphenyl, 2,4′-di (2-propenyl) biphenyl, 4,4′-di (2-propenyl) biphenyl, 2, 2'-divinyl-4-ethyl-4'-propylbiphenyl, 3,5,4'-trivinylbiff Non condensed polycyclic aromatic ring-containing polyfunctional monomer sulfonyl or the like may be used.

(Ethylenically unsaturated monomer polymer (C))
The polymer (C) derived from the ethylenically unsaturated monomer has an effect of ensuring the compatibility between the siloxane rubber polymer-containing multilayer structure polymer and the matrix resin according to the present invention. From the viewpoint of the expression of flame retardancy according to the present invention, the glass transition temperature of the polymer (C) is preferably 40 ° C or higher, more preferably 60 ° C or higher, and further preferably 90 ° C or higher.

  Such a polymer (C) derived from an ethylenically unsaturated monomer is a polymer obtained by polymerizing an ethylenically unsaturated monomer described later using a known radical polymerization method together with a chain transfer agent as necessary. It is a thing. When a polymer mixture containing the siloxane rubber polymer (A) and a polymer (B) having at least a unit derived from a polyfunctional monomer is obtained as an emulsion, the polymer (C) It is preferable to obtain by a legal method. Use of the chain transfer agent may improve the heat resistance and thermal stability of the resulting polyruganosiloxane-containing copolymer, the flame retardancy and impact resistance of the final molded product, and the like. Examples of such chain transfer agents include unsaturated terpenes, mercaptans, etc. Among them, the mercaptans are preferable, and the siloxane rubber polymer-containing multilayer structure polymer having no odor, or the resin composition according to the present invention. 2-ethylhexyl thioglycolate is most preferable since a product is obtained. The amount of the chain transfer agent used relative to the ethylenically unsaturated monomer depends on the graft efficiency of the polymer (C), the dispersibility of the siloxane rubber polymer-containing copolymer in the matrix resin, and the difficulty of the present invention. From the viewpoint of twistability and mechanical properties, it is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, further 0.1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less, further 2% by weight or less.

  Examples of the ethylenically unsaturated monomers include aromatic vinyl monomers such as styrene, α-methyl styrene, vinyl naphthalene, and vinyl biphenyl, vinyl cyanide monomers such as acrylonitrile, methyl acrylate, ethyl acrylate, Alkyls such as butyl acrylate, octyl acrylate, 21-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, lauryl methacrylate, myristyl methacrylate, stearyl methacrylate, behenyl methacrylate, benzyl methacrylate ( (Meth) acrylate, acrylamide, methacrylamide, dodecyl methacrylamide, cyclodo Sill methacrylamide, such as adamantyl methacrylamide (meth) acrylamide. In the present invention, unless otherwise specified, for example, (meth) acryl means acryl and / or methacryl.

  Among these monomers, preferred as the ethylenically unsaturated monomer is an aromatic vinyl such as styrene, α-methyl styrene, vinyl naphthalene, vinyl biphenyl from the viewpoint of flame retardancy according to the present invention. Type monomers, vinyl cyanide monomers such as acrylonitrile, alkyl (meth) acrylates having 2 or less carbon atoms in the alkyl group such as methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate, and more preferably , When only a monomer having a glass transition temperature of 40 ° C. or higher, more preferably 60 ° C. or higher, and further 90 ° C. or higher is used. Monomethylstyrene, vinylnaphthalene, vinylbiphenyl, acrylonitrile, methacrylonite Ril, methyl methacrylate and the like.

  As necessary for such preferable monomers, carboxyl group-containing vinyl monomers such as itaconic acid, (meth) acrylic acid, fumaric acid, maleic acid, 4-styrenesulfonic acid, 2-acrylamide-2- Sulphonic acid group-containing vinyl monomers such as methylpropane sulfonic acid or sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, organic phosphonium salts, organic sulfonium salts, organic ammonium salts, glycidyl methacrylate, etc. Functional group-containing vinyl compounds such as epoxy group-containing vinyl monomers, oxetane ring-containing vinyl monomers such as oxetane methacrylate, and hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl methacrylate and 4-hydroxybutyl acrylate A monomer can also be used in combination.

(Epoxy group-containing monomer polymer (D))
Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, and glycidyl methacrylate is preferable. In the present invention, unless otherwise specified, for example, (meth) acryl means acryl and / or methacryl.

(Combination agent)
The compounding agent used normally can be suitably added to the resin composition of this invention. Such additives include anti-dripping agents, phosphorus-based flame retardants, flame retardant aids, fiber reinforcing agents, fillers, antioxidants, colorants, pigments, conductivity imparting agents, heat conductivity imparting agents, hydrolysis Inhibitors, thickeners, plasticizers, lubricants, UV absorbers, antistatic agents, fluidity improvers, mold release agents, compatibilizers, coupling agents between fillers and matrix resins, thermal stabilizers, sliding And a property-imparting agent.

  In particular, when the resin composition of the present invention is used for a fuel tank, it is preferable to add carbon black to prevent electrification, and the preferable amount in this case is 0.1 to 10 parts by weight, more preferably 1 ~ 5 parts by weight.

(Molded product)
The molded product obtained from the resin composition of the present invention can be used as a member for housing / building materials, electrical / electronic applications, automotive applications, etc., but has excellent impact resistance, flame resistance, cold resistance, and chemical resistance. Therefore, it is preferably used as a member for automobiles, more preferably used as a container for liquid organic matter, for example, suitably used as a fuel tank. In this case, preferably, an upper part and a lower part of the tank are separately formed by injection molding. The fuel tank is made of a single material by molding and bonding.

  The liquid organic material is preferably one or more selected from the group consisting of alcohols, alkanes, alkenes, alkynes, alicyclic hydrocarbons, and aromatic hydrocarbons, more preferably aromatic hydrocarbons 29 to It is a gasoline composed of 36%, alkene 9-18%, saturated hydrocarbon 51-55%, and bioethanol high blended gasoline to which ethanol is added.

(Molding method)
As a molding method of the resin composition of the present invention, an injection molding method, an extrusion molding method, a blow molding method, a calendar molding method, an inflation molding method, a rotational molding method, or the like can be applied.

  Hereinafter, examples that more specifically represent the present invention will be described, but the present invention is not limited to these examples. In addition, the following measurement and test were performed as follows.

(Volume average particle diameter)
The volume average particle size of the seed polymer, siloxane rubber polymer particles, and multilayer structure polymer was measured in a latex state. The volume average particle diameter (μm) was measured using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd. as a measuring device.

(Weight average molecular weight)
The polymer was made into an approximately 0.2% tetrahydrofuran (THF) solution, and the solution was subjected to gel permeation chromatography (GPC) analysis to determine the weight average molecular weight (Mw). In the GPC analysis, an HLC-8220GPC system manufactured by Tosoh Corp. was used, and TSK Guardcolumn super HZ-H and TSKgel Super HZM-H (manufactured by Tosoh Corp.) were used as the column. We analyzed with.

(Impact resistance)
In accordance with ASTM D-256, the Izod test was used for evaluation. Specifically, it measured at 23 degreeC, -10 degreeC, and -40 degreeC using the 1 / 4-inch molded article sample and 2.75J hammer. The number of samples in each measurement was 4, and the average value was taken as the evaluation result.

(chemical resistance)
The weight change rate before and after immersion was measured for a sample obtained by injection molding and a sample which was immersed in toluene at room temperature for 4 days and then air-dried for 0.5 hour.

(Example of production of siloxane rubber polymer particles)
200 parts by weight of ion-exchanged water, 1 part by weight of alkylbenzene sulfonate (SDBS) having an average alkyl group chain length of 12, 1 part by weight of dodecylbenzene sulfonate (DBSA), and terminal dihydroxypolydimethylsiloxane (DHPDMS) having an average molecular weight of 2000 A mixture comprising 97.5 parts by weight and 2.5 parts by weight of γ-methacryloyloxypropylmethyldimethoxysilane (DSMA) was stirred with a homomixer at 10,000 rpm for 5 minutes, and then passed through a high-pressure homogenizer three times at a pressure of 500 bar. To prepare a siloxane emulsion. This emulsion was quickly charged all at once into a 5-ro-flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. The system was reacted at 30 ° C. for 6 hours while stirring the system. Then, after cooling to 23 ° C. and leaving for 20 hours, the pH of the system was adjusted to 6.8 with a 3% by weight aqueous sodium hydrogen carbonate solution to complete the polymerization, and a latex containing siloxane rubber polymer particles was obtained. The polymerization conversion rate was 97%, the volume average particle diameter of the latex of the siloxane rubber polymer particles was 0.28 μm, and the weight average molecular weight of the siloxane rubber polymer component was 230,000.

(Production Example 1: Production of siloxane rubber polymer-containing multilayer structure polymer (SG-1))
In a 5 b flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 240 parts by weight of ion-exchanged water (including the carry-in from latex containing organosiloxane particles), and above 70 parts by weight corresponding to the solid content of the latex of the siloxane rubber polymer particles obtained in the above was charged, and the temperature was raised to a polymerization temperature of 60 ° C. in a nitrogen stream while stirring the system. One hour after reaching that temperature, 0.25 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.002 parts by weight of ethylenediaminetetraacetate (EDTA), and 0.0005 parts by weight of ferrous sulfate were added. After the addition, a mixture consisting of 1 part by weight of triallyl isocyanurate (TAIC) and 0.05 part by weight of cumene hydroperoxide (CHP) was added all at once, and stirring was continued for 30 minutes.

  Thereafter, 0.04 part by weight of cumene hydroperoxide was further added and stirred for 30 minutes, and then 10 parts by weight of glycidyl methacrylate (GMA), 0.04 part by weight of 2-ethylhexyl thioglycolate (2EHTG), and CHP. A mixture of 1 part by weight was added dropwise at an additional rate of 20 parts by weight / hour, followed by 20 parts by weight of methyl methacrylate (MMA), 0.08 part by weight of 2-ethylhexyl thioglycolate (2EHTG), and CHP. Siloxane rubber by adding 2 parts by weight of the mixture dropwise at an additional rate of 20 parts by weight, followed by further stirring for 2 hours, followed by addition of 0.05 parts by weight of CHP and continued stirring for 30 minutes. A latex of the polymer-containing multilayer structure polymer (SG-1) was obtained. The polymerization conversion rate of all graft components was 100%, and the volume average particle diameter of the latex was 0.30 μm.

  The latex which has been heated to 70 ° C. and sprayed in a mist form is brought into contact with a 10 wt% calcium chloride aqueous solution which has been heated to 90 ° C. and sprayed in a mist form so that the solid content is equivalent to 4 parts by weight. Obtained. The obtained coagulated slurry is heated to 95 ° C. by steam heating, held for 5 minutes, cooled to 50 ° C., dehydrated, washed twice with 15 times the amount of resin and dried to contain a siloxane rubber polymer A powder of multilayer structure polymer SG-1 was obtained.

  Table 1 compares the composition of each layer of each sample obtained in Production Examples 1 to 6 and the steam heating temperature that is the maximum temperature during powder production.

(Production Example 2: Production of siloxane rubber polymer-containing multilayer structure polymer (SG-2))
A siloxane rubber polymer-containing multilayer structure polymer (SG-2) was produced in the same manner as in Production Example 1 except that the steam heating temperature 95 ° C. in Production Example 1 was changed to 90 ° C.

(Production Example 3: Production of siloxane rubber polymer-containing multilayer structure polymer (SG-3))
A siloxane rubber polymer-containing multilayer structure polymer (SG-3) was produced in the same manner as in Production Example 1 except that the amount of TAIC added in Production Example 1 was 0.5 part by weight.

(Production Example 4: Production of siloxane rubber polymer-containing multilayer structure polymer (SG-4))
A siloxane rubber polymer-containing multilayer structure polymer (SG-4) was produced in the same manner as in Production Example 1 except that the amount of TAIC added in Production Example 1 was 2 parts by weight.

(Production Example 5: Production of siloxane rubber polymer-containing multilayer structure polymer (SG-5))
In a 5 b flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 240 parts by weight of ion-exchanged water (including the carry-in from latex containing organosiloxane particles), and above 85 parts by weight of the latex of the siloxane rubber polymer particles obtained in the above was charged in an amount corresponding to the solid content, and the temperature was raised to a polymerization temperature of 60 ° C. in a nitrogen stream while stirring the system. One hour after reaching that temperature, 0.25 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.002 parts by weight of ethylenediaminetetraacetate (EDTA), and 0.0005 parts by weight of ferrous sulfate were added. After the addition, a mixture consisting of 2 parts by weight of triallyl isocyanurate (TAIC) and 0.05 parts by weight of cumene hydroperoxide (CHP) was added all at once, and stirring was continued for 30 minutes.

  Thereafter, 0.04 part by weight of cumene hydroperoxide was further added and the mixture was stirred for 30 minutes, then 2 parts by weight of glycidyl methacrylate (GMA), 13 parts by weight of methyl methacrylate (MMA), 2-ethylhexylthioglycolate (2EHTG) Add 0.06 parts by weight of the mixture and 0.145 parts by weight of CHP dropwise at an additional rate of 20 parts by weight / hour, then continue stirring for another 2 hours, and then add another 0.05 parts by weight of CHP. The latex of the siloxane rubber polymer-containing multilayer structure polymer (SG-6) was obtained by continuing the stirring for a minute. The polymerization conversion rate of all graft components was 100%, and the volume average particle diameter of the latex was 0.30 μm.

  The latex which has been heated to 70 ° C. and sprayed in a mist form is brought into contact with a 10 wt% calcium chloride aqueous solution which has been heated to 90 ° C. and sprayed in a mist form so that the solid content is equivalent to 4 parts by weight. Obtained. The obtained coagulated slurry is heated to 95 ° C. by steam heating, held for 5 minutes, cooled to 50 ° C., dehydrated, washed twice with 15 times the amount of resin and dried to contain a siloxane rubber polymer A powder of multilayer structure polymer SG-5 was obtained.

(Production Example 5: Production of siloxane rubber polymer-containing multilayer structure polymer (SG-6))
In a 5 b flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port and thermometer, 240 parts by weight of ion-exchanged water (including the carry-in from latex containing organosiloxane particles), and above 85 parts by weight of the latex of the siloxane rubber polymer particles obtained in the above was charged in an amount corresponding to the solid content, and the temperature was raised to a polymerization temperature of 60 ° C. in a nitrogen stream while stirring the system. One hour after reaching that temperature, 0.25 parts by weight of sodium formaldehyde sulfoxylate (SFS), 0.002 parts by weight of ethylenediaminetetraacetate (EDTA), and 0.0005 parts by weight of ferrous sulfate were added. After the addition, a mixture consisting of 2 parts by weight of triallyl isocyanurate (TAIC) and 0.05 parts by weight of cumene hydroperoxide (CHP) was added all at once, and stirring was continued for 30 minutes.

  Thereafter, 0.04 part by weight of cumene hydroperoxide was further added and the mixture was stirred for 30 minutes, then 15 parts by weight of methyl methacrylate (MMA), 0.06 part by weight of 2-ethylhexyl thioglycolate (2EHTG), and CHP 0. Siloxane rubber by adding 145 parts by weight of the mixture dropwise at an additional rate of 20 parts by weight per hour, followed by another 2 hours of stirring, followed by addition of 0.05 parts by weight of CHP and continued stirring for 30 minutes. A latex of a polymer-containing multilayer structure polymer (SG-5) was obtained. The polymerization conversion rate of all graft components was 100%, and the volume average particle diameter of the latex was 0.30 μm.

  The latex which has been heated to 70 ° C. and sprayed in a mist form is brought into contact with a 10 wt% calcium chloride aqueous solution which has been heated to 90 ° C. and sprayed in a mist form so that the solid content is equivalent to 4 parts by weight. Obtained. The obtained coagulated slurry is heated to 95 ° C. by steam heating, held for 5 minutes, cooled to 50 ° C., dehydrated, washed twice with 15 times the amount of resin and dried to contain a siloxane rubber polymer A powder of multilayer structure polymer SG-6 was obtained.

(Example 11, Comparative Examples 1-9)
A resin composition obtained by adding a powder of a multilayered polymer with the composition shown in Table 2 to 100 parts by weight of a linear PPS resin (FZ-2100 manufactured by DIC Corporation) is a twin-screw extruder (TEX44SS manufactured by Nippon Steel Works). ) And kneaded at 300 ° C. to produce pellets. Using the obtained pellets, a test piece for evaluation of impact resistance and chemical resistance having a thickness of ¼ inch was manufactured using a FAS100B injection molding machine manufactured by FANUC Corporation set to a cylinder temperature of 300 ° C. It evaluated according to the said evaluation method using the obtained test piece. The evaluation results are shown in Table 2.

  MBS1 in Table 2 is a butadiene / styrene rubber polymer-containing multilayer structure polymer having a methyl methacrylate having a volume average particle size of 0.08 μm as a shell layer.

  MBS2 in Table 2 is a butadiene-styrene rubber polymer-containing multilayer structure polymer having a methyl methacrylate having a volume average particle diameter of 0.30 μm as a shell layer.

  AM1 in Table 2 is a multilayer structure polymer containing a butyl acrylate rubber polymer having a methyl methacrylate having a volume average particle size of 0.20 μm as a shell layer.

  As shown in Table 2, the molded product of the resin composition of the present invention is excellent in mechanical strength and chemical resistance.

Claims (5)

A polyphenylene sulfide resin composition comprising 100 parts by weight of a polyphenylene sulfide resin and 5 to 50 parts by weight of a siloxane rubber polymer-containing multilayer structure polymer,
A rubber core layer comprising 100% by weight of the siloxane rubber polymer-containing multilayer structure polymer of 60 to 90% by weight of the siloxane rubber polymer (A), and a polyfunctional monomer-based polymer (B) 0 covering the rubber core layer .1-10 wt% hard intermediate layer, covering the hard intermediate layer, ethylenically unsaturated monomer polymer (C) 0-34.9 wt%, and epoxy group-containing monomer polymer (D) A polyphenylene sulfide resin composition comprising a shell layer comprising 5 to 30% by weight.   The shell layer comprises a reactive shell layer composed of 5 to 20% by weight of the epoxy group-containing monomer polymer (D), and the ethylenically unsaturated monomer polymer (C) composed of 14.9% to 34.34. A polyphenylene sulfide resin composition comprising two layers of a reactive control shell layer comprising 9% by weight.   The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin is a polyphenylene sulfide resin.   The molded object formed by shape | molding the polyphenylene sulfide type-resin composition in any one of Claims 1-3.   A container for liquid organic matter comprising the molded article according to claim 4.