JP2019167534A - Thermoplastic resin composition and molded article - Google Patents

Abstract

To provide a thermoplastic resin composition capable of easily producing a molded article excellent in all of color development, weather resistance, scuff resistance, and scratch resistance.SOLUTION: The thermoplastic resin composition of the present invention contains a graft copolymer (E), a graft copolymer (F), and a polymethacrylic acid ester (G). The content of the graft copolymer (E) is 4 mass% or more and 15 mass% or less based on 100 mass% of the thermoplastic resin composition. The graft copolymer (E) is a copolymer obtained by graft-polymerizing a vinyl-based monomer mixture (m1) containing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of an ethylene/α-olefin copolymer (a). The graft copolymer (F) is a copolymer obtained by graft-polymerizing one or more vinyl-based monomers (m2) in the presence of a composite rubbery polymer (d).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition and a molded article.

By improving the scratch resistance of the resin material, it becomes possible to keep the surface state of the molded article good, and the industrial utility such as the automobile field and the electric / electronic equipment field becomes very high. Therefore, various techniques have been studied so far for improving the scratch resistance of resin materials. For example, by using a thermoplastic resin composition such as an AES (acrylonitrile-ethylene / α-olefin-styrene) resin, many methods for improving the scratch resistance and slidability of molded products have been incorporated (for example, patents). References 1-3).
As a technique for improving the color development and weather resistance in addition to the scratch resistance of the molded article, it was used in combination with a composite rubber (hereinafter also referred to as “SAS resin”) of polyorganosiloxane and an alkyl (meth) acrylate polymer. Resins have been proposed (see, for example, Patent Documents 4 to 6).
However, in the above method, it is necessary to add a large amount of AES resin in order to improve the scratch resistance of the molded product. When a large amount of AES resin is blended, the color developability and weather resistance of the molded product tend to decrease.
Moreover, adding another silicone oil to AES resin as another method of improving the slidability and scratch resistance of a molded product has been proposed (see, for example, Patent Documents 7 to 11).

JP, 2006-186001, A Japanese Patent Laid-Open No. 2006-128540 International Publication No. 2013/132722 Japanese Patent Laying-Open No. 2015-96576 JP 2014-177623 A Republished WO2016 / 6567 JP 2012-158630 A JP 2012-158623 A JP 2011-178944 A Japanese Patent Laid-Open No. 2001-40160 JP 2000-302936 A

However, the methods described in Patent Documents 1 to 11 can improve one or two of the color developability, weather resistance and scratch resistance, but cannot improve all the color developability, weather resistance and scratch resistance. There wasn't. In particular, in the methods described in Patent Documents 4 to 8 in which silicone is added, since silicone oil bleeds out, there is a difficulty in sustaining scratch resistance. Therefore, the conventional AES resin molded product cannot sufficiently satisfy the required performance in the vehicle interior / exterior material or office equipment. Here, the scratch resistance includes scratch resistance and scratch resistance.
An object of this invention is to provide the thermoplastic resin composition which can manufacture easily the molded article which is excellent in all of coloring property, a weather resistance, an abrasion resistance, and a scratch resistance. Another object of the present invention is to provide a molded article excellent in all of color developability, weather resistance, scratch resistance, and scratch resistance.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising a graft copolymer (E), a graft copolymer (F), and a polymethacrylic acid ester (G), wherein the graft copolymer The content ratio of the union (E) is 4% by weight to 15% by weight with respect to 100% by weight of the thermoplastic resin composition, and the graft copolymer (E) is an ethylene / α-olefin copolymer. A copolymer obtained by graft polymerization of a vinyl monomer mixture (m1) containing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of (a), wherein the graft copolymer In the presence of the composite rubber-like polymer (d) in which the polyorganosiloxane (b) and the alkyl (meth) acrylate polymer (c) are combined, the blend (F) is one or more kinds of vinyl monomers. Obtained by graft polymerization of body (m2) A copolymer, wherein the ethylene · alpha-olefin copolymer (a) has a density less than 0.870 g / cm ³ or more 0.912 g / cm ^3, a volume average particle diameter is more than 0.2 [mu] m 0. 4 μm or less, the gel content is 3% by mass or less, the composite rubber-like polymer (d) has a volume average particle diameter of 0.1 μm or more and 0.2 μm or less, and the composite rubber-like polymer ( The proportion of particles having a particle diameter of 0.3 μm or more and 0.5 μm or less in all particles d) is 5% by volume or more and 25% by volume or less.
The molded article of the present invention contains the thermoplastic resin composition.

According to the thermoplastic resin composition of the present invention, it is possible to easily produce a molded product having excellent color developability, weather resistance, scratch resistance, and scratch resistance.
The molded product of the present invention is excellent in all of color developability, weather resistance, scratch resistance, and scratch resistance.

It is the schematic explaining the abrasion-resistance test in an Example and a comparative example.

"Thermoplastic resin composition"
Hereinafter, an embodiment of the thermoplastic resin composition of the present invention will be described.
The thermoplastic resin composition of this embodiment contains a graft copolymer (E), a graft copolymer (F), and a polymethacrylic acid ester (G). If necessary, the thermoplastic resin composition of this embodiment can be used as a graft copolymer (E), a graft copolymer (F), and a polymethacrylic acid ester (G) as long as the effects of the present invention are not impaired. In addition, an additive may be further contained.
A molded article can be produced by molding the thermoplastic resin composition of this embodiment.

<Graft copolymer (E)>
The graft copolymer (E) is a copolymer obtained by graft polymerization of the vinyl monomer mixture (m1) in the presence of the ethylene / α-olefin copolymer (a).
The graft copolymer (E) is a graft product in which a branch polymer composed of a polymer of a vinyl monomer mixture (m1) is bonded to a trunk polymer composed of a particulate ethylene / α-olefin copolymer (a). And a non-grafted product made of a polymer of the vinyl monomer mixture (m1).
In the graft copolymer (E), it is difficult to specify how the vinyl monomer mixture (m1) is polymerized with the ethylene / α-olefin copolymer (a). That is, there is a situation (impossible / unpractical situation) that the graft copolymer (E) cannot be directly specified by its structure or characteristics, or is almost impractical. Therefore, the graft copolymer (E) is defined as “a copolymer obtained by graft polymerization of the vinyl monomer mixture (m1) in the presence of the ethylene / α-olefin copolymer (a)”. It is more appropriate to do.

(Ethylene / α-olefin copolymer (a))
The ethylene / α-olefin copolymer (a) comprises an ethylene unit and an α-olefin unit obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms by a known polymerization method. It is a copolymer.
Examples of the α-olefin include propylene, 1-octene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-icosene and 1-docosene. Among the α-olefins, α-olefins having 3 to 20 carbon atoms are preferable, and propylene and 1-octene are more preferable from the viewpoint of scratch resistance and scratch resistance of the molded product.

The ethylene / α-olefin copolymer (a) may contain non-conjugated diene units. When the ethylene / α-olefin copolymer (a) contains a non-conjugated diene unit, the scratch resistance and scratch resistance of the molded article are more excellent.
Non-conjugated dienes include, for example, dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene and the like can be mentioned. Among the non-conjugated dienes, at least one of dicyclopentadiene and 5-ethylidene-2-norbornene is preferable in that the molded article obtained is more excellent in scratch resistance and scratch resistance.

  The ethylene unit content in the ethylene / α-olefin copolymer (a) is 45% when the total of all the structural units constituting the ethylene / α-olefin copolymer (a) is 100% by mass. % To 80% by mass is preferable, and 50% to 75% by mass is more preferable. When the ethylene unit content in the ethylene / α-olefin copolymer (a) is within the above range, the scratch resistance and scratch resistance of the molded article are further improved.

The density of the ethylene / α-olefin copolymer (a) in this embodiment is 0.870 g / cm ³ or more and 0.912 g / s because the scratch resistance and scratch resistance of the thermoplastic resin composition are good. preferably less than cm ^3, less than 0.900 g / cm ³ or more 0.905 g / cm ³ is more preferable. In addition, a density is measured based on JISK7112.

The ethylene / α-olefin copolymer (a) in this embodiment has a low gel content, and specifically 3% by mass or less. When the gel content of the ethylene / α-olefin copolymer (a) is 3% by mass or less, the color developability, weather resistance, scratch resistance, and scratch resistance of the molded product can be improved.
The gel content of the ethylene / α-olefin copolymer (a) may be 0% by mass, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
The gel content in the present invention is measured as follows.
The ethylene / α-olefin copolymer (a) is immersed in toluene, and the insoluble matter not dissolved in toluene is dried. And the ratio (unit: mass%) of the dried toluene insoluble content with respect to the mass of the ethylene-alpha-olefin copolymer (a) before toluene immersion is calculated. The calculated value is the gel content. A more specific method for measuring the gel content will be described in Examples described later.

The method for producing the ethylene / α-olefin copolymer (a) is not limited. The ethylene / α-olefin copolymer (a) is usually produced by copolymerizing ethylene and α-olefin or ethylene, α-olefin and non-conjugated diene using a metallocene catalyst or Ziegler-Natta catalyst. Is done.
As a metallocene catalyst, a catalyst obtained by combining an organic compound having a cyclopentadienyl skeleton with a transition metal (zirconium, titanium, hafnium, etc.), a metallocene complex in which a halogen atom or the like is coordinated, an organoaluminum compound, an organoboron compound, etc. Is mentioned.
Examples of the Ziegler-Natta catalyst include a catalyst in which a halide of a transition metal (titanium, vanadium, zirconium, hafnium, etc.) is combined with an organic aluminum compound, an organic boron compound, or the like.
Examples of the polymerization method include a method in which ethylene and an α-olefin, or ethylene, an α-olefin, and a nonconjugated diene are copolymerized in a solvent in the presence of the catalyst.
Examples of the solvent include hydrocarbon solvents (benzene, toluene, xylene, pentane, hexane, heptane, octane, etc.). A hydrocarbon solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it. Further, the raw material α-olefin itself may be used as a solvent.
By changing the reaction conditions such as the supply amount of ethylene, α-olefin and non-conjugated diene, the type and amount of molecular weight regulators such as hydrogen, the type and amount of catalyst, the reaction temperature, pressure, etc. The ethylene unit content, mass average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polymer (a) can be adjusted.

When producing the graft copolymer (E), an aqueous olefin resin dispersion (B) in which the ethylene / α-olefin copolymer (a) is dispersed in an aqueous dispersion may be used.
The aqueous olefin resin dispersion (B) is obtained by dispersing the ethylene / α-olefin copolymer (a) in an aqueous medium containing at least 50% by mass of water.
The preparation method of the olefin resin aqueous dispersion (B) is not limited. As an example of the preparation method of the aqueous olefin resin dispersion (B), the ethylene / α-olefin copolymer (a) is melt-kneaded by a known melt-kneading means (kneader, Banbury mixer, multi-screw extruder, etc.). And a method of adding to an aqueous medium containing an emulsifier by applying mechanical shearing force and dispersing.
As another example of the preparation method of the olefin resin aqueous dispersion (B), the ethylene / α-olefin copolymer (a) is added to a hydrocarbon solvent (pentane, hexane, heptane, benzene, toluene, xylene, etc.) together with an emulsifier. There is a method in which after dissolving, adding to an aqueous medium and emulsifying, the mixture is sufficiently stirred and the hydrocarbon solvent is distilled off.

In preparing the aqueous olefin resin dispersion (B), as other components, for example, an emulsifier, an acid-modified olefin polymer, and the like may be added.
Examples of the emulsifier include known ones, and examples thereof include long-chain alkyl carboxylates, sulfosuccinic acid alkyl ester salts, and alkylbenzene sulfonates.
The addition amount of the emulsifier is preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the ethylene / α-olefin copolymer (a). If the addition amount of the emulsifier is within the above range, thermal coloring of the resulting thermoplastic resin composition can be suppressed, and the ethylene / α-olefin copolymer (a) dispersed in the aqueous olefin resin dispersion (B). The particle diameter can be easily controlled.
As the acid-modified olefin polymer, an olefin polymer (polyethylene, polypropylene, etc.) having a mass average molecular weight of 1,000 or more and 5,000 or less is modified with a compound having a functional group (such as an unsaturated carboxylic acid compound). Can be mentioned. Examples of the unsaturated carboxylic acid compound include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, maleic acid monoamide, and the like.
The addition amount of the acid-modified olefin polymer is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the ethylene / α-olefin copolymer (a). When the amount of the acid-modified olefin polymer added is within the above range, the scratch resistance and scratch resistance of the molded product are further improved.
The method for adding the acid-modified olefin polymer is not limited. For example, after the acid-modified olefin polymer is added to the ethylene / α-olefin copolymer (a), a crosslinking treatment may be performed, or the ethylene / α-olefin copolymer (a) and the acid-modified olefin polymer These may be mixed after the crosslinking treatment.
The mixing method of the ethylene / α-olefin copolymer (a) and the acid-modified olefin polymer is not limited. Examples of the mixing method include a melt kneading method using a kneader, a Banbury mixer, a multi-screw extruder and the like.

The volume average particle diameter of the ethylene / α-olefin copolymer (a) constituting the aqueous dispersion of olefin resin (B) is from the viewpoint of excellent scratch resistance, scratch resistance and weather resistance of the molded product. It is 2 μm or more and 0.4 μm or less, and preferably 0.2 μm or more and 0.3 μm or less. When the volume average particle diameter of the ethylene / α-olefin copolymer (a) is 0.2 μm or more and 0.4 μm or less, the scratch resistance, scratch resistance, and weather resistance of the molded product are increased. When the volume average particle diameter of the ethylene / α-olefin copolymer (a) is smaller than 0.2 μm, the scratch resistance and scratch resistance of the molded product may be lowered. When the average particle diameter of the ethylene / α-olefin copolymer (a) is larger than 0.4 μm, the weather resistance of the molded product may be lowered.
The volume average particle diameter of the ethylene / α-olefin copolymer (a) is measured by a dynamic light scattering method. The average particle diameter of the ethylene / α-olefin copolymer (a) constituting the aqueous olefin resin dispersion (B) is the average particle size of the ethylene / α-olefin copolymer (a) in the thermoplastic resin composition as it is. The diameter is confirmed by image analysis using an electron microscope.
As a method for controlling the average particle diameter of the ethylene / α-olefin copolymer (a) dispersed in the aqueous olefin resin dispersion (B), the type or amount of the emulsifier, the type of the acid-modified olefin polymer, or Examples thereof include a method of adjusting the content, shearing force applied during kneading, temperature conditions, and the like.

(Vinyl monomer mixture (m1))
The vinyl monomer mixture (m1) polymerized to the ethylene / α-olefin copolymer (a) is a vinyl monomer mixture containing an aromatic vinyl monomer and a vinyl cyanide monomer. The vinyl monomer mixture (m1) may contain a vinyl monomer other than the aromatic vinyl monomer and the vinyl cyanide monomer.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinyl xylene, pt-butylstyrene, and ethylstyrene. From the viewpoint of scratch resistance and scratch resistance of the molded article, the aromatic vinyl monomer is preferably styrene or α-methylstyrene. An aromatic vinyl monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the aromatic vinyl monomer is preferably 60% by mass to 85% by mass, and more preferably 62% by mass to 80% by mass with respect to 100% by mass of the vinyl monomer mixture (m1). When the content of the aromatic vinyl monomer is within the above range, the scratch resistance and scratch resistance of the molded product are further improved.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. A vinyl cyanide monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the vinyl cyanide monomer is preferably 15% by mass or more and 40% by mass or less, and more preferably 20% by mass or more and 38% by mass or less with respect to 100% by mass of the vinyl monomer mixture (m1). When the content of the vinyl cyanide monomer is within the above range, the scratch resistance and scratch resistance of the molded product are further improved.

Examples of other vinyl monomers include acrylic acid esters (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, propyl methacrylate, Butyl methacrylate, etc.) and maleimide compounds (N-cyclohexylmaleimide, N-phenylmaleimide, etc.). Another vinyl-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of other vinyl monomers is preferably 30% by mass or less, and more preferably 10% by mass or less with respect to 100% by mass of the vinyl monomer mixture (m1).

(Production method of graft copolymer (E))
The graft copolymer (E) is produced by polymerizing the vinyl monomer mixture (m1) in the presence of the ethylene / α-olefin copolymer (a).
The graft copolymer (E) is an ethylene / α-olefin copolymer (a) in the presence of 50% by mass to 80% by mass, and the vinyl monomer mixture (m1) is 20% by mass to 50% by mass. However, a copolymer obtained by polymerizing an ethylene / α-olefin copolymer (a) and a vinyl monomer mixture (m1) is 100% by mass) is preferable. When the ethylene / α-olefin copolymer (a) is 50% by mass or more and 80% by mass or less, the color developability, scratch resistance, and scratch resistance of the molded product are further improved.

Examples of the polymerization method for producing the graft copolymer (E) include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc.). Among the polymerization methods, an emulsion polymerization method is preferable.
As a method for producing the graft copolymer (E) by the emulsion polymerization method, for example, after mixing an organic peroxide with the vinyl monomer mixture (m1), the vinyl monomer mixture (m1) The method of adding continuously to an olefin resin aqueous dispersion (B) is mentioned. The vinyl monomer mixture (m1) added to the aqueous olefin resin dispersion (B) is graft-polymerized to the ethylene / α-olefin copolymer (a) dispersed in the aqueous olefin resin dispersion (B). To do.

The organic peroxide is preferably used as a redox initiator that combines an organic peroxide, a transition metal, and a reducing agent. In the polymerization, a chain transfer agent, an emulsifier or the like may be used depending on the situation.
The redox initiator is preferably a combination of an organic peroxide and a ferrous sulfate-chelating agent-reducing agent. By using such a combination of redox initiators, the polymerization temperature can be made relatively low, the deterioration of the ethylene / α-olefin copolymer (a) can be prevented, and the deterioration of the weather resistance of the molded product is further avoided. it can.
Examples of the organic peroxide include cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, and the like.
The redox initiator is more preferably composed of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose.

Examples of chain transfer agents include mercaptans (octyl mercaptan, n- or t-dodecyl mercaptan, n-hexadecyl mercaptan, n- or t-tetradecyl mercaptan, etc.), allyl compounds (allylsulfonic acid, methallylsulfonic acid). And sodium salts thereof), α-methylstyrene dimer, and the like. Among the chain transfer agents, mercaptans are preferable because the molecular weight can be easily adjusted. The said chain transfer agent may be used individually by 1 type, and may be used in combination of 2 or more type.
The method for adding the chain transfer agent may be any of batch, split, and continuous.
The addition amount of the chain transfer agent is preferably 2.0 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m1).

Examples of the emulsifier include anionic surfactants, nonionic surfactants, and amphoteric surfactants.
Examples of the anionic surfactants include higher alcohol sulfates, alkylbenzene sulfonates, fatty acid sulfonates, phosphate salts, fatty acid salts, and amino acid derivative salts.
Examples of nonionic surfactants include ordinary polyethylene glycol alkyl ester types, alkyl ether types, and alkyl phenyl ether types.
Examples of the amphoteric surfactant include those having a carboxylate salt, sulfate ester salt, sulfonate salt, phosphate ester salt and the like in the anion portion and amine salts and quaternary ammonium salts in the cation portion.
The amount of the emulsifier added is preferably 10 parts by mass or less with respect to 100 parts by mass of the vinyl monomer mixture (m1).

The graft copolymer (E) obtained by the emulsion polymerization method is in a state of being dispersed in water. As a method for recovering the graft copolymer (E) from the aqueous dispersion containing the graft copolymer (E), for example, a precipitation agent is added to the aqueous dispersion, heated and stirred, and then the precipitation agent is separated. And a precipitation method in which the precipitated graft copolymer (E) is washed, dehydrated and dried.
Examples of the precipitating agent include aqueous solutions of sulfuric acid, acetic acid, calcium chloride, magnesium sulfate, and the like. A precipitation agent may be used individually by 1 type, and may be used in combination of 2 or more type.
An antioxidant may be added to the aqueous dispersion containing the graft copolymer (E) as necessary.

As a method for producing the graft copolymer (E) by the solution polymerization method, for example, an inert polymerization solvent used in ordinary radical polymerization is used. Examples of the inert polymerization solvent include aromatic hydrocarbons such as ethylbenzene and toluene, ketones such as methyl ethyl ketone and acetone, and halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride.
As the polymerization initiator used for the solution polymerization, a general initiator is used. For example, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and hydroperoxide are used. Moreover, the method of adding a polymerization initiator collectively or continuously is mentioned.

<Graft copolymer (F)>
The graft copolymer (F) is a copolymer obtained by graft polymerization of one or more vinyl monomers (m2) in the presence of the composite rubber-like polymer (d).
The graft copolymer (F) includes a graft product in which a branch polymer composed of a polymer of a vinyl monomer (m2) is bonded to a trunk polymer composed of a particulate composite rubber-like polymer (d), and a vinyl based monomer. And a non-grafted product made of a polymer of a monomer (m2).
In the graft copolymer (F), it is difficult to specify how the vinyl monomer (m2) is polymerized in the composite rubber-like polymer (d). That is, there is a situation (impossible / unpractical situation) that the graft copolymer (F) cannot be directly specified by its structure or characteristics, or is almost impractical. Therefore, the graft copolymer (F) is defined as “a copolymer obtained by graft polymerization of one or more vinyl monomers (m2) in the presence of the composite rubber-like polymer (d)”. It is more appropriate to do.

(Composite rubbery polymer (d))
The composite rubber-like polymer (d) is a composite rubber in which the polyorganosiloxane (b) and the alkyl (meth) acrylate polymer (c) are combined.
The ratio of the polyorganosiloxane (b) and the alkyl (meth) acrylate polymer (c) in the composite rubber-like polymer (d) is not particularly limited, but because the color development and weather resistance of the molded product are more excellent, When the total of the polyorganosiloxane (b) and the alkyl (meth) acrylate polymer (c) is 100% by mass, the ratio of the polyorganosiloxane (b) is 4% by mass or more and 14% by mass or less. Is preferred.

The composite rubber-like polymer (d) is in a granular form and is present in a granular form in the thermoplastic resin composition.
The volume average particle diameter of the composite rubber-like polymer (d) is from 0.1 μm to 0.2 μm, and preferably from 0.12 μm to 0.18 μm. When the volume average particle diameter of the composite rubber-like polymer (d) is not less than the lower limit of the above range, the color developability of the molded product is excellent. When the volume average particle diameter of the composite rubber-like polymer (d) is not more than the upper limit of the above range, the weather resistance of the molded product is excellent.
Here, the volume average particle size of the composite rubber-like polymer (d) is measured by measuring the volume-based particle size distribution of the composite rubber-like polymer (d) using a dynamic light scattering type particle size distribution analyzer. It is a value calculated from the obtained particle size distribution.

In the composite rubber-like polymer (d), the proportion of the particles having a particle diameter of 0.3 μm or more and 0.5 μm or less in the total particles of the composite rubber-like polymer (d) is 5% by volume or more and 25% by volume or less. It is. That is, the composite rubber-like polymer (d) has a particle size distribution (volume basis) in which particles having a particle size of 0.3 μm or more and 0.5 μm or less occupy a ratio of 5% by volume to 25% by volume in all particles. Have. When the proportion of particles having a particle size of 0.3 μm or more and 0.5 μm or less is 5% by volume or more, the color development of the molded product is excellent, and when it is 25% by volume or less, the weather resistance of the molded product is excellent. . Since the balance between color developability and weather resistance of the molded product becomes better, the proportion of particles having a particle size of 0.3 μm or more and 0.5 μm or less may be 5% by volume or more and 15% by volume or less. preferable.
Further, the proportion of the particles having a particle diameter of more than 0.5 μm in the total particles in the composite rubber-like polymer (d) is less than 1% by volume from the viewpoint that the weather resistance of the molded product becomes better. Preferably, it is less than 0.1% by volume.

Here, the ratio of particles having a particle diameter of 0.3 μm or more and 0.5 μm or less and the ratio of particles having a particle diameter of more than 0.5 μm are combined using a dynamic light scattering particle size distribution analyzer. It is a value calculated from the particle size distribution obtained by measuring the volume-based particle size distribution of the rubber-like polymer (d).
The volume-based particle size distribution of the composite rubber-like polymer (d) is a value for all the composite rubber-like polymers (d) contained in the thermoplastic resin composition. Therefore, the volume average particle diameter, the ratio of particles having a particle diameter of 0.3 μm or more and 0.5 μm or less, and the ratio of particles having a particle diameter of more than 0.5 μm are all composites included in the thermoplastic resin composition. This is the value for the entire rubber-like polymer (d).
The volume average particle diameter of the composite rubber-like polymer (d) and the proportion of the particles having a particle diameter of 0.3 μm or more and 0.5 μm or less are the same as the volume of the composite rubber-like polymer (d) in the thermoplastic resin composition. It was confirmed by image analysis of an electron micrograph that the average particle size and the particle size were 0.3 μm or more and 0.5 μm or less.

  In the thermoplastic resin composition of this embodiment, when two or more kinds of graft copolymers (F) are contained, the volume average particle diameter and the ratio of the particles having a particle diameter of 0.3 μm or more and 0.5 μm or less as a whole Is within the above range. If it is within the range, the composite rubber-like polymer whose volume average particle size is outside the above range in the two or more types of graft copolymers (F), or the particle size is 0.3 μm or more and 0.5 μm or less. A graft copolymer (F) having a composite rubber-like polymer in which the proportion of the particles is outside the above range may be contained.

[Polyorganosiloxane (b)]
The polyorganosiloxane (b) constituting the composite rubber-like polymer (d) is not particularly limited, but a polyorganosiloxane containing a vinyl polymerizable functional group (vinyl polymerizable functional group-containing polyorganosiloxane) is preferable, A polyorganosiloxane having a vinyl polymerizable functional group-containing siloxane unit and a dimethylsiloxane unit is more preferred.
Examples of the vinyl polymerizable functional group include a methacryloyloxyalkyl group, an acryloyloxyalkyl group, a vinyl group, and a vinyl-substituted phenyl group. The carbon number of the alkyl group in the methacryloyloxyalkyl group and acryloyloxyalkyl group may be, for example, 1 or more and 12 or less.
The vinyl polymerizable functional group-containing siloxane unit may have an organic group other than the vinyl polymerizable functional group. Examples of other organic groups include an alkyl group such as a methyl group and a phenyl group.
The content of the vinyl polymerizable functional group-containing siloxane unit is preferably 0.3 mol% or more and 3 mol% or less with respect to the total number of moles (100 mol%) of all units constituting the polyorganosiloxane (b). When the content of the vinyl polymerizable functional group-containing siloxane unit is within the above range, the polyorganosiloxane (b) and the alkyl (meth) acrylate polymer (c) are sufficiently complexed to form poly on the surface of the molded product. The organosiloxane (b) is difficult to bleed out. Therefore, the weather resistance of the molded product is further improved.
In the polyorganosiloxane (b), since the color developability of the molded article is further improved, the content of silicon atoms having three or more siloxane bonds is the total moles of all silicon atoms in the polyorganosiloxane (b). It is preferably more than 0 mol% and 1 mol% or less with respect to the number (100 mol%).

  As a preferred embodiment of the polyorganosiloxane (b), 0.3 mol% or more and 3 mol% or less of vinyl polymerizable functional group-containing siloxane units and 99.7 mol% or more and 97 mol% or less of dimethylsiloxane units (however, vinyl polymerization) The content of silicon atoms having 3 or more siloxane bonds is 1 mol with respect to the total number of moles of all silicon atoms. % Or less of polyorganosiloxane.

The average particle diameter of the polyorganosiloxane (b) is not particularly limited, but is preferably 0.4 μm or less and more preferably 0.15 μm or less because the weather resistance of the molded product is further improved. About a lower limit, 0.02 micrometer or more is preferable.
Here, the average particle size of the polyorganosiloxane (b) is a value calculated from a particle size distribution obtained by measuring a mass-based particle size distribution using a dynamic light scattering type particle size distribution measuring instrument ( Mass average particle diameter).

[Production Method of Polyorganosiloxane (b)]
The polyorganosiloxane (b) can be obtained, for example, by polymerizing a siloxane mixture containing a dimethylsiloxane oligomer and a vinyl polymerizable functional group-containing siloxane.

  As the dimethylsiloxane oligomer, a dimethylsiloxane ring having 3 or more members is preferable, and a dimethylsiloxane ring having 3 to 7 members is more preferable. Specific examples of the dimethylsiloxane oligomer include, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These dimethylsiloxanes may be used alone or in combination of two or more.

The vinyl polymerizable functional group-containing siloxane is not particularly limited as long as it contains a vinyl polymerizable functional group and can be bonded to a dimethylsiloxane oligomer via a siloxane bond. Among the vinyl polymerizable functional group-containing siloxanes, an alkoxysilane compound containing a vinyl polymerizable functional group is preferable in consideration of reactivity with the dimethylsiloxane oligomer.
Specific examples of the alkoxysilane compound containing a vinyl polymerizable functional group include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, and γ-methacryloyloxy. Methacryloyloxysiloxanes such as propyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane; tetramethyltetravinylcyclotetrasiloxane, p-vinyl Vinyl siloxanes such as phenyldimethoxymethylsilane; and the like. These vinyl polymerizable functional group-containing siloxanes may be used alone or in combination of two or more.

The method for polymerizing the siloxane mixture is not particularly limited, but emulsion polymerization is preferred. Emulsion polymerization is usually performed using an emulsifier, water, and an acid catalyst.
As the emulsifier, an anionic emulsifier is preferable. Specific examples include sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable. These emulsifiers may be used alone or in combination of two or more.
The amount of the emulsifier is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the siloxane mixture. If the usage-amount of an emulsifier is 0.05 mass part or more, the dispersion state of a siloxane mixture will be easy to be stabilized, and it will become easy to hold | maintain the emulsification state of a fine particle diameter. On the other hand, if the usage-amount of an emulsifier is 5 mass parts or less, the deterioration of the weather resistance resulting from an emulsifier can be suppressed.

Examples of the acid catalyst include organic acid catalysts such as sulfonic acids (eg, aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, aliphatic substituted naphthalene sulfonic acid, etc.); inorganic acids such as mineral acids (eg, sulfuric acid, hydrochloric acid, nitric acid, etc.) A catalyst etc. are mentioned. These acid catalysts may be used alone or in combination of two or more.
Among these, aliphatic substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable in that it is excellent in the stabilizing action of the siloxane latex (e) described later. In addition, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the influence of the color of the emulsifier used in the production of the polyorganosiloxane (b) on the color of the molded product can be suppressed.
The addition amount of the acid catalyst may be appropriately determined, but is usually about 0.1 to 20 parts by mass with respect to 100 parts by mass of the siloxane mixture.

The acid catalyst may be mixed with the siloxane mixture, the emulsifier and water at the timing of mixing them, or the siloxane mixture, the emulsifier and water are mixed and emulsified to form a latex (siloxane latex (e)). (E) may be finely divided and then mixed with the finely divided siloxane latex (e).
Since it is easy to control the particle diameter of the resulting polyorganosiloxane (b), it is preferable that the siloxane latex (e) and the acid catalyst are mixed after the siloxane latex (e) is finely divided. In particular, it is preferable that the finely divided siloxane latex (e) is dropped into the acid catalyst aqueous solution at a constant rate.
When the acid catalyst is mixed at the timing of mixing the siloxane mixture, the emulsifier, and water, it is preferable to make the particles fine after mixing them.
Siloxane latex (e) can be formed into fine particles by using, for example, a homomixer or a homogenizer. A homomixer performs microparticulation with a shearing force generated by high-speed rotation. The homogenizer atomizes with a jet output from a high pressure generator.
Examples of the method of mixing the siloxane mixture, the emulsifier, water and the acid catalyst, and the method of mixing the finely divided siloxane latex (e) and the acid catalyst include mixing by high-speed stirring, mixing by a high-pressure emulsifier such as a homogenizer, etc. Is mentioned. Among these, a method using a homogenizer is preferable because the particle size distribution of the polyorganosiloxane (b) can be reduced.

The polymerization temperature when polymerizing the siloxane mixture is preferably 50 ° C. or higher, and more preferably 80 ° C. or higher. In addition, when dripping the micronized siloxane latex (e) into the acid catalyst aqueous solution, the temperature of the acid catalyst aqueous solution is preferably 50 ° C. or higher, and preferably 80 ° C. or higher.
The polymerization time is preferably 2 hours or longer, and more preferably 5 hours or longer when the acid catalyst is mixed at the timing of mixing the siloxane mixture, the emulsifier and water. In the case of mixing the finely divided siloxane latex (e) and the acid catalyst, it is preferable that the finely divided siloxane latex (e) is dropped into the acid catalyst aqueous solution and then held for about 1 hour.
To stop the polymerization, after cooling the reaction solution, the reaction solution is neutralized with an alkaline substance such as sodium hydroxide, potassium hydroxide, or sodium carbonate so that the pH of the reaction solution is about 6 or more and 8 or less. Can be done.
As described above, a latex of polyorganosiloxane (b) is obtained.
The average particle size of the polyorganosiloxane (b) can be controlled by adjusting the composition of the siloxane mixture, the amount of the acid catalyst used (the content of the acid catalyst in the acid catalyst aqueous solution), the polymerization temperature, and the like. For example, the average particle size tends to increase as the amount of the acid catalyst used decreases, and the average particle size tends to decrease as the polymerization temperature increases.

[Alkyl (meth) acrylate polymer (c)]
The alkyl (meth) acrylate polymer (c) constituting the composite rubber-like polymer (d) is a polymer having an alkyl (meth) acrylate unit. “Alkyl (meth) acrylate” is a general term for alkyl acrylate or alkyl methacrylate.
The (meth) acrylate polymer may further have a monomer (other monomer) unit other than the alkyl (meth) acrylate unit.
Carbon number of the alkyl group of the alkyl (meth) acrylate may be 1 or more and 12 or less, for example.
Examples of alkyl (meth) acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; hexyl methacrylate, 2-methacrylic acid 2- Examples include methacrylic acid alkyl esters such as ethylhexyl and n-lauryl methacrylate. These alkyl (meth) acrylates may be used individually by 1 type, and may use 2 or more types together. Among the alkyl (meth) acrylates, n-butyl acrylate is preferable in that the weather resistance of the molded product is further improved.
The other monomer is not particularly limited as long as it can be copolymerized with alkyl (meth) acrylate. For example, aromatic vinyl compounds (for example, styrene, α-methylstyrene, p-methylstyrene, etc.), cyanide Examples thereof include vinyl compounds (for example, acrylonitrile, methacrylonitrile, etc.). These other monomers may be used individually by 1 type, and may use 2 or more types together.
In the alkyl (meth) acrylate polymer (c), the content of the alkyl (meth) acrylate unit is preferably 80% by mass or more and 100% by mass or less based on the total mass of all monomer units, 90 More preferably, it is at least 100% by mass.
The alkyl (meth) acrylate polymer (c) is obtained by polymerizing a monomer component containing at least one alkyl (meth) acrylate. This monomer component may contain other monomers.
The polymerization method of the monomer component is not particularly limited, and can be performed according to a known method.

(Method for producing composite rubber-like polymer (d))
The method for producing the composite rubber-like polymer (d) is not particularly limited, but a plurality of latexes each containing the polyorganosiloxane (b) and the alkyl (meth) acrylate polymer (c) are hetero-aggregated or co- enlarged. A method comprising: polymerizing a monomer component forming the other polymer in the presence of a latex containing one of the polyorganosiloxane (b) and the alkyl (meth) acrylate polymer (c) to form a composite. And the like.
Since the volume average particle size and particle size distribution of the composite rubber-like polymer (d) can be easily adjusted so as to be within the above-described ranges, the alkyl (meth) in the presence of the latex polyorganosiloxane (b). By mixing the monomer component containing one or more acrylates by radical polymerization to obtain a copolymer latex (radical polymerization step), the copolymer latex and the acid group-containing copolymer latex are mixed. A method having a step of enlarging the polymer latex (a hypertrophy step) is preferable. This method preferably further includes a step of adding a condensed acid salt to the copolymer latex (condensed acid salt adding step) after the radical polymerization step and before the enlargement step.

Radical polymerization process:
The radical polymerization step is a step of radical polymerization of a monomer component containing at least one alkyl (meth) acrylate in the presence of latex polyorganosiloxane (b).
The monomer component containing at least one alkyl (meth) acrylate may be added all at once to the latex polyorganosiloxane (b), or may be added continuously or intermittently.
When radically polymerizing a monomer component containing one or more alkyl (meth) acrylates, a graft crossing agent or a crosslinking agent may be used as necessary.
Examples of the grafting agent or cross-linking agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diglycolic acid ethylene glycol diester, dimethacrylic acid propylene glycol diester, dimethacrylic acid 1,3-butylene glycol diester. And 1,4-butylene glycol diester of dimethacrylic acid. These may be used individually by 1 type and may use 2 or more types together.
In radical polymerization, a radical polymerization agent and an emulsifier are usually used.
Examples of the radical polymerization initiator include peroxides, azo initiators, redox initiators in which an oxidizing agent and a reducing agent are combined. In these, a redox-type initiator is preferable and especially the sulfoxylate-type initiator which combined ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate, and hydroperoxide is preferable.
Although it does not restrict | limit especially as an emulsifier, since it is excellent in the stability of the latex at the time of radical polymerization and a polymerization rate can be raised, various carboxylic acids, such as sodium sarcosinate, fatty acid potassium, fatty acid sodium, alkenyl succinate dipotassium, rosin acid soap, etc. Salts are preferred. Among these, dipotassium alkenyl succinate is preferable because gas generation can be suppressed when the obtained graft copolymer (F) and the thermoplastic resin composition containing the graft copolymer (F) are molded at high temperature.
For example, the polymerization start temperature may be 40 ° C. or higher and 70 ° C. or lower, and the time from the start to the end of the polymerization may be 0.5 hours or longer and 3.0 hours or shorter.

Condensate addition process:
The condensed acid salt addition step is a step of adding a condensed acid salt to the copolymer latex obtained in the radical polymerization step. Prior to the enlargement process, by adding a condensation acid salt to the copolymer latex, it becomes possible to reduce the addition amount of the acid group-containing copolymer latex by making the enlargement easier to proceed, and the composite rubber It becomes easy to adjust the volume average particle size and particle size distribution of the polymer (d) within the above-described ranges.

As the condensed acid salt, for example, a salt of a condensed acid such as phosphoric acid or silicic acid and an alkali metal and / or alkaline earth metal is used. Among these, pyrophosphoric acid and alkali metal salts which are condensed acids of phosphoric acid are preferable, and sodium pyrophosphate or potassium pyrophosphate is particularly preferable.
The addition amount of the condensed acid salt may be adjusted so that the volume average particle size and particle size distribution of the composite rubber-like polymer (d) are within the above-mentioned ranges, but usually it is obtained in the radical polymerization step. It is preferable that it is 0.1 to 5 mass parts with respect to 100 mass parts of solid content of copolymer latex, and 0.3 to 3 mass parts is more preferable. If the amount of the condensed acid salt is not less than the lower limit of the above range, the enlargement is sufficiently advanced, and if it is not more than the upper limit of the above range, the enlargement is sufficiently advanced or the rubber latex is easily stabilized. , Generation of a large amount of agglomerates can be suppressed.
The condensed acid salt is preferably added to the copolymer latex all at once.
The pH of the copolymer latex to which the condensed acid salt is added (mixture of copolymer latex and condensed acid salt) at 25 ° C. is preferably 7 or more. If the pH is 7 or more, enlargement is likely to proceed sufficiently. In order to make pH 7 or more, general alkali compounds, such as sodium hydroxide and potassium hydroxide, can be used.

Enlargement process:
The enlargement process is obtained in the radical polymerization process, and if necessary, the copolymer latex to which the condensation salt is added in the condensation salt addition process and the acid group-containing copolymer latex are mixed. This is a step of enlarging the copolymer latex. Thereby, the latex of a composite rubber-like polymer (d) is obtained.

The acid group-containing copolymer has an acid group-containing monomer unit and an alkyl (meth) acrylate unit. Other monomer units other than these may further be included as necessary.
As the acid group-containing monomer, an unsaturated compound having a carboxy group is preferable. Examples of the unsaturated compound having a carboxy group include (meth) acrylic acid, itaconic acid, crotonic acid and the like, and (meth) acrylic acid is particularly preferable. (Meth) acrylic acid refers to acrylic acid or methacrylic acid. An acid group containing monomer may be used individually by 1 type, and may use 2 or more types together.
Examples of the alkyl (meth) acrylate include esters of (meth) acrylic acid and an alcohol having a linear or branched alkyl group having 1 to 12 carbon atoms. For example, methyl acrylate, ethyl acrylate, acrylic Propyl acid, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t -Butyl, 2-ethylhexyl methacrylate and the like. Among these, an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms is particularly preferable. Alkyl (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.
The other monomer is a monomer copolymerizable with the acid group-containing monomer and the alkyl (meth) acrylate, and is a monomer other than the acid group-containing monomer and the alkyl (meth) acrylate. . Other monomers include aromatic vinyl compounds (eg, styrene, α-methylstyrene, p-methylstyrene, etc.), vinyl cyanide compounds (eg, acrylonitrile, methacrylonitrile, etc.), two or more polymerizable Examples include compounds having a functional group (for example, allyl methacrylate, polyethylene glycol ester dimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitic acid, etc.). Another monomer may be used individually by 1 type and may use 2 or more types together.

  As an acid group containing copolymer, content of an acid group containing monomer unit is 5 mass% or more with respect to the total mass (100 mass%) of all the monomer units which comprise an acid group containing copolymer. A copolymer having a content of 40% by mass or less, an alkyl (meth) acrylate unit of 60% by mass to 95% by mass, and a content of another monomer unit of 0% by mass to 48% by mass is preferable. The content of acid group-containing monomer units is 8% by mass or more and 30% by mass or less, the content of alkyl (meth) acrylate units is 70% by mass or more and 92% by mass or less, and the content of other monomer units is 0%. A copolymer having a mass% of 30% by mass or less is more preferable. When the content of the acid group-containing monomer unit is not less than the lower limit and the content of the alkyl (meth) acrylate unit is not more than the upper limit, sufficient enlargement ability can be obtained. If the content of the acid group-containing monomer unit is not more than the above upper limit value and the content of the alkyl (meth) acrylate unit is not less than the above lower limit value, a large amount of coagulum is produced during the production of the acid group-containing copolymer latex. Can be suppressed. If the content of other monomer units is not more than the above upper limit value, the acid group-containing copolymer latex can have a sufficient enlargement ability.

Acid group-containing copolymer latex polymerizes monomer components containing acid group-containing monomers, alkyl (meth) acrylates, and, if necessary, other monomers copolymerizable with these in water. Is obtained. As the polymerization method, a general emulsion polymerization method can be used.
Examples of emulsifiers used in emulsion polymerization include carboxylic acid-based emulsifiers such as oleic acid, palmitic acid, stearic acid, alkali metal salts of rosin acid, and alkali metal salts of alkenyl succinic acid; alkyl sulfate esters, sodium alkylbenzene sulfonates, Known emulsifiers such as anionic emulsifiers such as sodium alkylsulfosuccinate and sodium polyoxyethylene nonylphenyl ether sulfate may be mentioned. These emulsifiers may be used alone or in combination of two or more.
The emulsifier may be added all at once in the initial stage of polymerization, or may be added continuously or intermittently. Depending on the amount of the emulsifier and its method of use, the particle size of the acid group-containing copolymer latex may eventually affect the particle size of the enlarged composite rubber-like polymer (d) latex. It is preferable to select the method of use.
Examples of the polymerization initiator used for emulsion polymerization include a thermal decomposition type initiator and a redox type initiator. Examples of the thermal decomposition type initiator include potassium persulfate, sodium persulfate, and ammonium persulfate. Examples of the redox-type initiator include combinations of organic peroxides represented by cumene hydroperoxide, sodium formaldehyde sulfoxylate, iron salts, and the like. These polymerization initiators may be used alone or in combination of two or more.
In the case of emulsion polymerization, a chain transfer agent such as mercaptans (for example, t-dodecyl mercaptan, n-octyl mercaptan, etc.), terpinolene, α-methylstyrene dimer, or the like is used to adjust the molecular weight. Therefore, an electrolyte can be added as an alkali, an acid, or a thickener.

The addition amount (solid content conversion amount) of the acid group-containing copolymer latex in the enlargement process is adjusted so that the volume average particle size and particle size distribution of the composite rubber-like polymer (d) are within the above-described ranges. Usually, the content is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.3 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the solid content of the copolymer latex obtained in the radical polymerization step. Is more preferable. If the addition amount of the acid group-containing copolymer latex is 0.1 parts by mass or more, enlargement proceeds sufficiently. Moreover, it can suppress that agglomerates generate | occur | produce in large quantities. On the other hand, if the addition amount of the acid group-containing copolymer latex is 5 parts by mass or less, the pH of the enlarged latex can be suppressed from being lowered, and the latex is less likely to become unstable.
The acid group-containing copolymer latex may be added to the copolymer latex all at once, or may be added continuously or intermittently by dropping.
It is preferable to appropriately control stirring during enlargement. If the stirring is insufficient, unextended rubbery polymer may remain due to local enlargement. On the other hand, if the stirring is performed excessively, the enlarged latex becomes unstable and a large amount of agglomerates may be generated.
The temperature at which the enlargement is performed is not particularly limited, but is preferably 20 ° C. or higher and 90 ° C. or lower, and more preferably 30 ° C. or higher and 80 ° C. or lower. If the temperature is outside this range, enlargement may not sufficiently proceed.
The composite rubber-like polymer (d) is enlarged using the acid group-containing copolymer latex as described above, and then a monomer component containing at least one alkyl (meth) acrylate is further added. You may manufacture by making it polymerize.

(Vinyl monomer (m2))
The vinyl monomer (m2) that is polymerized into the composite rubber-like polymer (d) is not particularly limited as long as it is a monomer having a vinyl group. The vinyl monomer (m2) is preferably at least one selected from the group consisting of an aromatic vinyl compound, a (meth) acrylic acid alkyl ester, and a vinyl cyanide compound.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and the like.
Examples of the (meth) acrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and the like. Is mentioned.
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
A vinyl-type monomer (m2) may be used individually by 1 type, and may use 2 or more types together.
In the vinyl monomer (m2), it is preferable to use styrene and acrylonitrile in combination since the color developability and weather resistance of the molded product are further improved.

(Production method of graft copolymer (F))
The graft copolymer (F) is obtained by graft polymerization of one or more vinyl monomers (m2) to the composite rubber-like polymer (d).
In the production of the graft copolymer (F), the mass ratio of the composite rubber-like polymer (d) and the vinyl monomer (m2) is not particularly limited. However, since the balance between color developability and weather resistance of the molded article becomes better, the composite rubber-like polymer (d) is 10% by mass to 80% by mass and the vinyl monomer (m2) is 20% by mass. The composite rubber-like polymer (d) is preferably 30% by mass to 70% by mass and the vinyl monomer (m2) is 30% by mass to 70% by mass. Is more preferable. However, the total of the composite rubber-like polymer (d) and the vinyl monomer (m2) is 100% by mass. If the mass ratio of the composite rubber-like polymer (d) and the vinyl monomer (m2) is within the above range, the color developability and weather resistance of the molded product are more excellent.

  The polymerization method for producing the graft copolymer (F) is not particularly limited, but emulsion polymerization is preferable because the reaction can be controlled to proceed stably. Specifically, a method in which a vinyl monomer (m2) is charged all at once to the latex of the composite rubber-like polymer (d) and then polymerized; a single monomer of vinyl to the latex of the composite rubber-like polymer (d) A method in which a part of the body (m2) is charged first and the remainder is dropped into the polymerization system while polymerizing as needed; while the total amount of the vinyl monomer (m2) is dropped into the latex of the composite rubber-like polymer (d) The method of superposing | polymerizing as needed is mentioned. These methods may be performed in one stage or two or more stages. When carrying out in two steps or more, the type and composition ratio of the vinyl monomers (m2) in each step may be the same or different.

In emulsion polymerization, a radical polymerization initiator and an emulsifier are usually used. Examples of the radical polymerization initiator and the emulsifier include a radical polymerization initiator and an emulsifier used when the graft copolymer (E) is produced.
In the polymerization, various known chain transfer agents may be added in order to control the molecular weight and graft ratio of the obtained graft copolymer (F).
The polymerization conditions may be, for example, a polymerization start temperature of 60 ° C. or more and 90 ° C. or less and a time from the start of polymerization to the end of 2.0 hours or more and 5.0 hours or less.

The graft copolymer (F) obtained by emulsion polymerization is usually in a latex state.
As a method for recovering the graft copolymer (F) from the latex of the graft copolymer (F), for example, the latex of the graft copolymer (F) is poured into hot water in which a coagulant is dissolved. A wet method of coagulating in a slurry state by spraying; a spray drying method of recovering the graft copolymer (F) semi-directly by spraying the latex of the graft copolymer (F) in a heated atmosphere.
Examples of the coagulant used in the wet method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid; metal salts such as calcium chloride, calcium acetate, and aluminum sulfate, and are selected according to the emulsifier used in the polymerization. . For example, when only a carboxylic acid soap such as fatty acid soap or rosin acid soap is used as an emulsifier, one or more of the above-described coagulants can be used. Further, when an emulsifier exhibiting a stable emulsifying power even in an acidic region such as sodium alkylbenzenesulfonate is used as the emulsifier, a metal salt is suitable as the coagulant.
When a wet method is used, a slurry-like graft copolymer (F) is obtained.

As a method for obtaining the dried graft copolymer (F) from the slurry-like graft copolymer (F), the remaining emulsifier residue is first eluted and washed in water, and then this slurry is centrifuged or press-dehydrated. Examples include a method of drying with an air dryer after dehydrating with a machine; a method of simultaneously performing dehydration and drying with a press dehydrator or an extruder. By this method, a powder or particulate dry graft copolymer (F) is obtained.
Although it does not restrict | limit especially as washing | cleaning conditions, It is wash | cleaned on the conditions from which the amount of emulsifier residues contained in 100 mass% of graft copolymers (F) after drying becomes the range of 0.5 mass% or more and 2 mass% or less. preferable. If the emulsifier residue in the graft copolymer (F) is 0.5% by mass or more, the fluidity of the obtained graft copolymer (F) and the thermoplastic resin composition containing the graft copolymer (F) tends to be further improved. . When the emulsifier residue in the graft copolymer (F) is 2% by mass or less, gas generation can be suppressed when the thermoplastic resin composition is molded at high temperature. The amount of the emulsifier residue can be adjusted by, for example, the washing time.
The drying temperature may be, for example, 60 ° C. or higher and 80 ° C. or lower.
The volume average particle size and volume-based particle size distribution of the composite rubber-like polymer (d) in the obtained graft copolymer (F) are determined by the composite rubber-like polymer used in the production of the graft copolymer (F). It is the same as the volume average particle size and volume-based particle size distribution of the composite rubber-like polymer (d) in the latex of the combined (d).
In addition, the graft copolymer (F) discharged | emitted from the press dehydrator and the extruder is not collect | recovered, but it is also possible to send directly to the extruder and molding machine which manufacture a resin composition, and to make a molded article.

<Polymethacrylic acid ester (G)>
The polymethacrylic acid ester (G) is a single polymer of one kind of methacrylic acid ester, a copolymer of two or more kinds of methacrylic acid esters, one or more other monomers other than methacrylic acid esters and methacrylic acid esters. And a copolymer with the body. Polymethacrylic acid ester (G) may be used individually by 1 type, and may use 2 or more types together.
Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, and phenyl methacrylate. Is mentioned.
Examples of monomers other than methacrylic acid esters include aromatic vinyl monomers, vinyl cyanide monomers, maleimide monomers, and (meth) acrylic acid. As the aromatic vinyl monomer and the vinyl cyanide monomer, the same monomers as those contained in the vinyl monomer mixture (m1) can be used.
As maleimide monomers, N-alkylmaleimides (N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Ni-butylmaleimide, N-t-butylmaleimide), N-cycloalkylmaleimide (N-cyclohexylmaleimide, etc.), N-arylmaleimide (N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, N-chlorophenylmaleimide, etc.) and the like.

Since the balance between color developability and weather resistance of the molded product becomes better, the polymethacrylic acid ester (G) is different from the polymethacrylic acid ester (G-1) and the polymethacrylic acid ester (G-1). It is preferable to use two types of polymethacrylic acid ester (G-2) in combination.
The two types of polymethacrylic acid ester (G-1) and polymethacrylic acid ester (G-2) are not particularly limited, and examples of the polymethacrylic acid ester (G-1) include homopolymers of methacrylic acid esters. Is mentioned. Specific examples of the polymethacrylic acid ester (G-1) include, for example, polymethyl methacrylate, polyethyl methacrylate, poly (n-propyl methacrylate), poly (i-propyl methacrylate), poly (n-butyl methacrylate), poly (methacrylic acid). Examples include i-butyl acid and poly-t-butyl methacrylate.
Examples of the polymethacrylic acid ester (G-2) include a copolymer of a methacrylic acid ester and a maleimide monomer. Specific examples of the polymethacrylic acid ester (G-2) include a copolymer of methacrylic acid ester and N-alkylmaleimide, and a copolymer of methacrylic acid ester and N-cycloalkylmaleimide. As the methacrylic acid ester, N-alkylmaleimide, and N-cycloalkylmaleimide, the above-described monomers can be used.
The mass ratio of the two types of polymethacrylic acid ester (G-1) and polymethacrylic acid ester (G-2) is not particularly limited, but the balance between the color developability and the weather resistance of the molded product becomes better. , (G-1) and (G-2) are 100% by mass, (G-1) is 20% by mass to 50% by mass, and (G-2) is 50% by mass or more. It is preferably 80% by mass or less, more preferably (G-1) is 30% by mass or more and 50% by mass or less, and (G-2) is 50% by mass or more and 70% by mass or less.

<Various additives>
Examples of the various additives include antioxidants, light stabilizers, lubricants, processing aids, pigments, fillers, silicone oils, paraffin oils, flame retardants, antistatic agents, and the like.

<Content of each component>
The content ratio of the graft copolymer (E) in the thermoplastic resin composition is 4% by mass or more and 15% by mass or less, and 4% by mass or more and 10% by mass or less with respect to 100% by mass of the thermoplastic resin composition. It is preferable. When the content ratio of the graft copolymer (E) is within the above range, the color developability, weather resistance, scratch resistance, and scratch resistance of the molded product are further improved.
The content ratio of the graft copolymer (F) in the thermoplastic resin composition is preferably 15% by mass or more and 35% by mass or less, and more preferably 18% by mass or more and 30% by mass with respect to 100% by mass of the thermoplastic resin composition. The following is more preferable. When the content ratio of the graft copolymer (F) is within the above range, the color developability, weather resistance, scratch resistance, and scratch resistance of the molded product are further improved.
The content ratio of the polymethacrylic acid ester (G) in the thermoplastic resin composition is preferably 40% by mass or more and 80% by mass or less, and 50% by mass or more and 70% by mass with respect to 100% by mass of the thermoplastic resin composition. The following is more preferable. When the content ratio of the polymethacrylic acid ester (G) is within the above range, the color developability, weather resistance, scratch resistance, and scratch resistance of the molded product are further improved.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition of the present embodiment is prepared by using, for example, a graft copolymer (E), a graft copolymer (F), a polymethacrylic acid ester (G), and an additive as necessary. It is manufactured by mixing and melt-kneading.
As the mixer, for example, a mixer such as a V-type blender or a Henschel mixer can be used. In the melt-kneading, a melt-kneader such as a screw extruder, a Banbury mixer, a pressure kneader, or a mixing roll can be used. After the melt-kneading, a pelletizer for pelletizing the strand discharged from the melt-kneader may be used.

<Effect>
The thermoplastic resin composition of the present embodiment described above is a graft copolymer obtained by graft polymerization of a vinyl monomer mixture (m1) in the presence of an ethylene / α-olefin copolymer (a) ( E), a graft copolymer (F) obtained by graft polymerization of a vinyl monomer (m2) in the presence of the composite rubber-like polymer (d), and a polymethacrylate (G). It is a composition to contain.
In this embodiment, the density of the ethylene · alpha-olefin copolymer constituting the graft copolymer (E) (a) is less than 0.870 g / cm ³ or more 0.912 g / cm ^3, the volume average particle diameter Is 0.2 μm or more and 0.4 μm or less, and the gel content is 3% by mass or less.
In this embodiment, the composite rubber-like polymer (d) constituting the graft copolymer (F) has a volume average particle diameter of 0.1 μm or more and 0.2 μm or less, and the composite rubber-like polymer (d) The proportion of particles having a particle diameter of 0.3 μm or more and 0.5 μm or less in the particles is 5% by volume or more and 25% by volume or less.
Since the graft copolymer (E) and the graft copolymer (F) are used in combination, the thermoplastic resin composition of this embodiment has any of color development, weather resistance, scratch resistance, and scratch resistance. Excellent molded products can be easily manufactured.

"Molding"
One aspect of the molded product of the present invention will be described.
The molded product of this aspect contains the thermoplastic resin composition of the said aspect.
Specifically, the molded article of this embodiment is produced by molding the thermoplastic resin composition of the above embodiment by a known molding method.
Examples of the molding method of the thermoplastic resin composition include an injection molding method, a press molding method, an extrusion molding method, a vacuum molding method, and a blow molding method.
Applications of the molded product of this aspect include vehicle interior parts, vehicle exterior parts, office equipment, home appliances, building materials, and the like.
In the molded product of this aspect, since the thermoplastic resin composition of the above aspect is used, all of color development, weather resistance, scratch resistance, and scratch resistance are excellent.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example. In the following examples, “%” and “part” are based on mass unless otherwise specified.
The measuring methods of the volume average particle diameter, gel content rate, and mass average molecular weight of the ethylene / α-olefin copolymer (a) in the following examples are as follows.

<Measurement of particle size distribution and volume average particle size of composite rubbery polymer (d)>
The volume-based particle size distribution of the composite rubber-like polymer (d) latex was measured using a nanotrack particle size distribution meter ("UPA-EX150" manufactured by Nikkiso Co., Ltd.) and using pure water as a measurement solvent. From the obtained particle size distribution, the volume average particle size and the ratio of particles having a particle size of 0.3 μm or more and 0.5 μm or less were determined. These can be regarded as the volume average particle diameter of the composite rubber-like polymer (d) in the thermoplastic resin composition and the ratio of particles having a particle diameter of 0.3 μm or more and 0.5 μm or less. Actually, the volume average particle diameter of the composite rubber-like polymer (d) and the ratio of the particles having a particle diameter of 0.3 μm or more and 0.5 μm or less are the same as in the composite rubber-like polymer ( It was confirmed by image analysis of an electron micrograph that the volume average particle size of d) and the proportion of particles having a particle size of 0.3 μm or more and 0.5 μm or less were shown.
In an example in which two types of graft copolymers (F) are used in combination, the volume average particle diameter and particle diameter of the composite rubber-like polymer (d) in the thermoplastic resin composition are set to 0. 0 by image analysis using an electron microscope. The proportion of particles of 3 μm or more and 0.5 μm or less was confirmed.

<Measurement of Volume Average Particle Diameter of Ethylene / α-Olefin Copolymer (a)>
The volume-based particle size distribution of the aqueous olefin resin dispersion (B) was measured using a nanotrack particle size distribution meter ("UPA-EX150" manufactured by Nikkiso Co., Ltd.) and using pure water as a measurement solvent. The measured volume average particle diameter can be regarded as the same as the volume average particle diameter of the ethylene / α-olefin copolymer (a) in the thermoplastic resin composition. Actually, the volume average particle diameter of the ethylene / α-olefin copolymer (a) measured by the measurement method is the volume average particle diameter of the ethylene / α-olefin copolymer (a) in the thermoplastic resin composition. It was confirmed by image analysis of electron micrographs.

<Measurement of ethylene / α-olefin copolymer (a) gel content>
To a mixed solution of 200 mL of methanol and 120 mL of 5% sulfuric acid aqueous solution, 10 mL of an aqueous dispersion or solvent dispersion of ethylene / α-olefin copolymer (a) was added and coagulated, followed by filtration through a 200 mesh wire net. Next, the coagulated material filtered in 200 mL of pure water was added and stirred for 20 minutes, and then the coagulated material was filtered through a 200 mesh wire net. The coagulated material filtered in 200 mL of methanol was added and stirred for 20 minutes, and then the coagulated material was filtered through a 200 mesh wire net. The obtained powdery solidified product was dried at 23 ° C. for 24 hours or more using a vacuum dryer. 0.5 g of the obtained coagulated powder sample [D1] was placed in a mesh basket, and 550 g of toluene was added. Toluene containing the coagulated powder sample was put into a separable flask, heated to a liquid temperature of 105 ° C. using a heater, and heated to reflux for 6 hours. Subsequently, it was cooled, the cooled mesh basket was taken out, and dried at room temperature for 24 hours or more using a vacuum dryer. The mass of the mesh basket after vacuum drying was measured, the mass of the dried product [D2] was measured, and the gel content of the ethylene / α-olefin copolymer (a) was determined from the following formula (1).
Gel content rate (%) = (Dry substance amount [D2] (g) / coagulated powder sample mass [D1] (g)) × 100 (1)

<Measurement method of mass average molecular weight (Mw)>
Using gel permeation chromatography (GPC: “GPC / V2000” manufactured by Waters, column: “ShodexAT-G + AT-806MS” manufactured by Showa Denko KK), the molecular weight was determined using o-dichlorobenzene (145 ° C.) as a solvent. It was measured. The mass average molecular weight (Mw) was calculated | required using the analytical curve created using the standard polystyrene with known molecular weight.

<Ethylene / α-olefin copolymer (a)>
(Ethylene / α-olefin copolymer (a-1))
“ENGAGE (engage) polyolefin elastomer, ENGAGE 8407” manufactured by The Dow Chemical Company was used as (a-1). Melting point 65 ° C., density 0.870 g / cm ³ .
(Ethylene / α-olefin copolymer (a-2))
“ENGAGE (engaged) polyolefin elastomer, ENGAGE 8402” manufactured by The Dow Chemical Company was used as (a-2). Melting point 99 ° C., density 0.902 g / cm ³ .
(Ethylene / α-olefin copolymer (a-3))
“NORDEL IP Hydrocarbon Rubber, NORDEL IP 4820P” manufactured by The Dow Chemical Company was used as (a-3). Melting point 90 ° C., density 0.910 g / cm ³ .
(Ethylene / α-olefin copolymer (a-4))
“Tafmer TP3180” manufactured by Mitsui Chemicals, Inc. was used as (a-4). Melting point 34 ° C., density 0.860 g / cm ³ .
(Ethylene / α-olefin copolymer (a-5))
“Ultzex 20200J” manufactured by Prime Polymer Co., Ltd. was used as (a-5). Melting point 120 ° C., density 0.918 g / cm ³ .

<Production Example 1: Production of Aqueous Olefin Resin Dispersion (B-1)>
100 parts of ethylene / α-olefin copolymer (a-1) and maleic anhydride-modified polyethylene (Mitsui Chemicals, “Mitsui High Wax 2203A”, mass average molecular weight: 2,700 as acid-modified olefin polymer) 25 parts of acid value: 30 mg / g) and 5 parts of potassium oleate (“KS soap” manufactured by Kao Corporation) as an emulsifier were mixed.
This mixture was supplied at 4 kg / h from the hopper of a twin screw extruder (“Ikegai Co., Ltd.,“ PCM30 ”, L / D = 40). While continuously supplying an aqueous solution in which 0.5 parts of potassium hydroxide and 3.5 parts of ion-exchanged water are supplied from the supply port provided in the vent part of the twin screw extruder, it is heated to 220 ° C. and melted. Kneaded and extruded. The obtained melt-kneaded product was continuously supplied to a cooling device attached to the tip of a twin screw extruder and cooled to 90 ° C. Then, the solid discharged from the tip of the twin screw extruder is poured into warm water at 80 ° C., continuously dispersed, diluted to a solid content concentration of around 40% by mass, and an aqueous olefin resin dispersion (B -1) was obtained. When the volume average particle diameter of the ethylene / α-olefin copolymer (a-1) in the thermoplastic resin composition was confirmed by an electron microscope, it was 0.22 μm. The gel content of the ethylene / α-olefin copolymer (a-1) was 2.5% by mass.

<Production Example 2: Production of Aqueous Olefin Resin Dispersions (B-2) to (B-5)>
As shown in Table 1, the olefin resin aqueous dispersions (B-2) to (B- 5) was obtained. Table 1 shows the volume average particle size and gel content of the aqueous olefin resin dispersions (B-2) to (B-5).

<Production Example 3: Production of Crosslinked Ethylene / α-Olefin Copolymer (C-1)>
Ion exchange water was added to the olefin resin aqueous dispersion (B-1) (100 parts as solid content) so that the solid concentration was 35%. Further, 1 part of t-butylcumyl peroxide as an organic peroxide and 1 part of divinylbenzene as a polyfunctional compound were added and reacted at 130 ° C. for 5 hours to obtain a crosslinked ethylene / α-olefin copolymer (C— 1) was prepared. Table 2 shows the volume average particle diameter and gel content of the crosslinked ethylene / α-olefin copolymer (C-1).

<Production Example 4: Production of crosslinked ethylene / α-olefin copolymers (C-2) to (C-3)>
As shown in Table 2, a crosslinked ethylene / α-olefin copolymer (C-2) was prepared in the same manner as in Production Example 3 except that the type of the olefin resin aqueous dispersion and the amount of t-butylcumyl peroxide were changed. ) To (C-3) were obtained. Table 2 shows the volume average particle diameter and gel content of the crosslinked ethylene / α-olefin copolymers (C-2) to (C-3).

<Production Example 5: Production of polyorganosiloxane (b)>
98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this was added an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of ion-exchanged water, and the mixture was stirred at 10,000 rpm for 2 minutes using a homomixer. Thereafter, the mixture was passed twice through a homogenizer at a pressure of 300 kg / cm ² to obtain a stable premixed organosiloxane latex.
Separately, 10 parts of dodecylbenzenesulfonic acid and 90 parts of ion-exchanged water were put into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, and a 10% aqueous solution of dodecylbenzenesulfonic acid ( Acid catalyst aqueous solution) was prepared.
This acid catalyst aqueous solution was heated to 85 ° C., and in this state, the premixed organosiloxane latex was added dropwise to the acid catalyst aqueous solution over 2 hours. After the completion of the addition, the temperature was maintained for 3 hours, and then cooled to 40 ° C. or lower. Next, the reaction product was neutralized with 10% aqueous sodium hydroxide solution to pH 7.0 to obtain a latex of polyorganosiloxane (b).
The obtained polyorganosiloxane (b) latex was dried at 180 ° C. for 30 minutes and the solid content was determined to be 18.2%. Moreover, the mass average particle diameter of the polyorganosiloxane (b) was 0.03 μm.

<Production Example 6: Production of acid group-containing copolymer latex (K-1)>
In a reactor equipped with a reagent injection container, a condenser tube, a jacket heater and a stirrer, 200 parts of ion-exchanged water, 2 parts of potassium oleate, 4 parts of sodium dioctylsulfosuccinate, ferrous sulfate heptahydrate 0.003 Part, 0.009 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of sodium formaldehyde sulfoxylate were charged under a nitrogen stream, and the temperature was raised to 60 ° C. When the temperature reached 60 ° C., a mixture composed of 85 parts of n-butyl acrylate, 15 parts of methacrylic acid and 0.5 part of cumene hydroperoxide was continuously added dropwise over 120 minutes. After completion of the dropwise addition, the mixture was further aged for 2 hours while maintaining the temperature at 60 ° C., and the solid content was 33%, the polymerization conversion was 96%, and the acid group-containing copolymer had a volume average particle size of 0.12 μm. A group-containing copolymer latex (K-1) was obtained.

<Production Example 7: Production of acid group-containing copolymer latex (K-2)>
Similar to Production Example 6 except that 1.5 parts of potassium oleate, 88 parts of n-butyl acrylate and 12 parts of methacrylic acid were changed, solid content was 33%, polymerization conversion was 97%, acid An acid group-containing copolymer latex (K-2) having a volume average particle size of the group-containing copolymer of 0.06 μm was obtained.

<Production Example 8: Production of graft copolymer (E-1)>
The aqueous olefin resin dispersion (B-1) was placed in a stainless polymerization tank equipped with a stirrer, and ion-exchanged water was added so that the solid concentration was 30%. Furthermore, 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were charged, and the temperature was set to 80 ° C. Here, the solid content of the ethylene / α-olefin copolymer (a) is 70 parts.
Next, 22.5 parts of styrene (indicated as “ST” in the table), 7.5 parts of acrylonitrile (indicated as “AN” in the table), and 0.6 part of cumene hydroperoxide in the polymerization vessel. Was continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. This obtained the aqueous dispersion of the graft copolymer (E-1) containing the ethylene-alpha-olefin copolymer (a-1) with a volume average particle diameter of 0.22 micrometer.
An antioxidant is added to the aqueous dispersion of the graft copolymer (E-1), the solid content is precipitated by addition of sulfuric acid, and after washing, dehydration and drying steps, the powdered graft copolymer (E- 1) was obtained.
The ethylene / α-olefin copolymer (a-1) in the thermoplastic resin composition in which the volume average particle diameter of the ethylene / α-olefin copolymer in the graft copolymer (E-1) was also measured by an electron microscope. It is confirmed that the volume average particle diameter is the same.

<Production Example 9: Production of graft copolymers (E-2) to (E-5)>
As shown in Table 3, graft copolymers (E-2) to (E-5) were obtained in the same manner as in Production Example 8, except that the type of the olefin resin aqueous dispersion was changed.

<Production Example 10: Production of graft copolymer (E-6)>
The cross-linked ethylene / α-olefin copolymer (C-1) was placed in a stainless polymerization tank equipped with a stirrer, and ion-exchanged water was added so that the solid content concentration was 30%. Furthermore, 0.006 part of ferrous sulfate, 0.3 part of sodium pyrophosphate and 0.35 part of fructose were charged, and the temperature was set to 80 ° C. Here, the solid content of the ethylene / α-olefin copolymer (a) is 70 parts.
Subsequently, 22.5 parts of styrene, 7.5 parts of acrylonitrile and 0.6 part of cumene hydroperoxide were continuously added for 150 minutes, and the polymerization temperature was kept at 80 ° C. to carry out emulsion polymerization. As a result, an aqueous dispersion of a graft copolymer (E-6) containing an ethylene / α-olefin copolymer having a volume average particle diameter of 0.22 μm was obtained.
An antioxidant is added to the aqueous dispersion of the graft copolymer (E-6), solid content is precipitated by addition of sulfuric acid, and after washing, dehydration, and drying steps, the powdered graft copolymer (E- 6) was obtained.
The ethylene / α-olefin copolymer (a-1) in the thermoplastic resin composition in which the volume average particle diameter of the ethylene / α-olefin copolymer in the graft copolymer (E-6) was also measured by an electron microscope. It is confirmed that the volume average particle diameter is the same.

<Production Example 11: Production of graft copolymers (E-7) to (E-8)>
As shown in Table 4, graft copolymers (E-7) to (E-8) were obtained in the same manner as in Production Example 10 except that the type of the crosslinked ethylene / α-olefin copolymer was changed.

<Production Example 12: Production of graft copolymer (F-1)>
In a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer, 5.0 parts of latex of polyorganosiloxane (b) in terms of solid content, 0.6 parts of dipotassium alkenyl succinate, 190 parts of ion exchange water was charged and mixed. Next, 45.0 parts of n-butyl acrylate (indicated as “BA” in Table 5) as a monomer constituting the alkyl (meth) acrylate polymer (c), allyl methacrylate (in Table 5) 0.6 parts, 1,3-butylene glycol dimethacrylate (indicated as “BGDMA” in Table 5) 0.09 parts, t-butyl hydroperoxide 0.02 parts The resulting mixture was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the internal temperature was raised to 60 ° C. When the internal temperature reached 60 ° C., from 0.000075 part of ferrous sulfate heptahydrate, 0.00023 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of sodium formaldehyde sulfoxylate, 10 parts of ion-exchanged water The resulting aqueous solution was added to initiate radical polymerization. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., and the polymerization is continued until the polymerization exotherm is not confirmed. A latex was obtained (radical polymerization step). The obtained composite rubber had a volume average particle size of 0.09 μm.
After the liquid temperature inside the reactor dropped to 70 ° C., 0.20 part of 5% aqueous sodium pyrophosphate solution was added as a solid content (condensate addition step). Next, after controlling at an internal temperature of 70 ° C., 0.26 parts of acid group-containing copolymer latex (K-1) is added as a solid content, stirred for 30 minutes, enlarged, and composite rubber-like polymer (d ) Latex was obtained (the enlargement process).
The obtained latex-like composite rubbery polymer (d) had a volume average particle size of 0.15 μm. Moreover, the ratio of the particle | grains whose particle diameters are 0.3 micrometer or more and 0.5 micrometer or less in all the particles of a composite rubber-like polymer (d) was 15 volume%.
To the latex of the composite rubber-like polymer (d), 0.001 part of ferrous sulfate heptahydrate, 0.003 part of disodium ethylenediaminetetraacetic acid, 0.3 part of sodium formaldehyde sulfoxylate, 10 parts of ion-exchanged water An aqueous solution consisting of parts was added. Subsequently, a mixed liquid composed of 8.8 parts of acrylonitrile, 26.2 parts of styrene, and 0.16 part of t-butyl hydroperoxide was dropped over 80 minutes to perform polymerization. After completion of the dropwise addition, after maintaining the temperature at 75 ° C. for 30 minutes, a mixture comprising 3.8 parts of acrylonitrile, 11.2 parts of styrene, 0.07 part of t-butyl hydroperoxide and 0.02 part of n-octyl mercaptan Was added dropwise over 20 minutes to polymerize. After completion of dropping, after maintaining the temperature at 75 ° C. for 30 minutes, 0.05 part of cumene hydroperoxide was added, and after maintaining the temperature at 75 ° C. for 30 minutes, the mixture was cooled, and a composite rubber polymer ( A latex of a graft copolymer (F-1) based on a silicone / acrylic composite rubber obtained by graft polymerization of acrylonitrile and styrene on d) was obtained.
Subsequently, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (F-1) was gradually dropped therein to be solidified. Then, the precipitate was separated, dehydrated, washed and dried to obtain a graft copolymer (F-1).

<Production Example 13: Production of graft copolymers (F-2) to (F-10)>
As shown in Table 5, the amount of allyl methacrylate and 1,3-butylene glycol dimethacrylate used in the radical polymerization step, the amount of sodium pyrophosphate used in the enlargement step, and the type of acid group-containing copolymer latex And the graft copolymers (F-2) to (F-10) were obtained in the same manner as in Production Example 12 except that the amount was changed.

<Production Example 14: Production of graft copolymer (F-11)>
In a reactor equipped with a reagent injection container, a condenser, a jacket heater, and a stirrer, 6.0 parts of latex of polyorganosiloxane (b) in terms of solid content, 0.1 part of sodium dodecylbenzenesulfonate, Then, 190 parts of ion-exchanged water was charged and mixed. Next, as a monomer constituting the alkyl (meth) acrylate polymer (c), 44.0 parts of n-butyl acrylate, 0.4 part of allyl methacrylate, 0.09 part of 1,3-butylene glycol dimethacrylate, A mixture consisting of 0.12 parts of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the internal temperature was raised to 60 ° C. When the internal temperature reached 60 ° C., from 0.000075 part of ferrous sulfate heptahydrate, 0.00023 part of ethylenediaminetetraacetic acid disodium salt, 0.2 part of sodium formaldehyde sulfoxylate, 10 parts of ion-exchanged water The resulting aqueous solution was added to initiate radical polymerization. After the polymerization exotherm is confirmed, the jacket temperature is set to 75 ° C., and the polymerization is continued until the polymerization exotherm is not confirmed. A latex was obtained (radical polymerization step). The obtained composite rubber had a volume average particle size of 0.09 μm.
An aqueous solution consisting of 0.2 part of sodium formaldehyde sulfoxylate and 10 parts of ion-exchanged water was added to the latex of the composite rubber-like polymer (d). Subsequently, a mixed liquid composed of 2.5 parts of acrylonitrile, 7.5 parts of styrene, and 0.1 part of t-butyl hydroperoxide was dropped over 20 minutes to polymerize. After completion of the dropwise addition, the temperature was maintained at 75 ° C. for 30 minutes, and then a mixture composed of 10 parts of acrylonitrile, 30 parts of styrene and 0.2 part of t-butyl hydroperoxide was dropped over 80 minutes for polymerization. After completion of dropping, after maintaining the temperature at 75 ° C. for 30 minutes, 0.05 part of cumene hydroperoxide was added, and after maintaining the temperature at 75 ° C. for 30 minutes, the mixture was cooled, and a composite rubber polymer ( A latex of a graft copolymer (F-11) based on a silicone / acrylic composite rubber obtained by graft polymerization of acrylonitrile and styrene on d) was obtained.
Subsequently, 150 parts of a 1% calcium acetate aqueous solution was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (F-11) was gradually dropped into the solution to be solidified. Then, the precipitate was separated, dehydrated, washed and dried to obtain a graft copolymer (F-11).

The volume average particle diameter of the composite rubber-like polymer (d) used for the production of the graft copolymers (F-1) to (F-11), the particle diameter occupying in all the particles is 0.3 μm or more and 0.5 μm. Table 5 shows the ratio of the following particles.
In Table 5, “AN” is acrylonitrile and “ST” is styrene.

<Polymethacrylic acid ester (G)>
(Polymethacrylic acid ester (G-1))
“Polyimilex PML203” (N-phenylmaleimide / N-cyclohexylmaleimide / methyl methacrylate / styrene copolymer, mass average molecular weight 200,000) manufactured by Nippon Shokubai Co., Ltd. was used as the polymethacrylate ester (G-1). .
(Polymethacrylic acid ester (G-2))
"Acrypet VH5" (Methyl methacrylate unit 98 mass%, methacrylic acid unit 2 mass%, mass average molecular weight 6,900) manufactured by Mitsubishi Chemical Corporation was used as the polymethacrylic acid ester (G-2).

<Examples and Comparative Examples>
Graft copolymers and polymethacrylic acid esters (G) shown in Tables 6 to 8, 1.0 part of EBS-WAX (manufactured by Kao Corporation), 0.4 part of ADK STAB LA-31 (manufactured by ADEKA Corporation), Then, 0.4 part of ADK STAB LA-63PK (manufactured by ADEKA Corporation) and 0.8 part of carbon black were mixed using a Henschel mixer. The obtained mixture was subjected to a cylinder temperature of 200 ° C. or higher and 260 ° C. or lower and 93.325 kPa vacuum using a screw type extruder (manufactured by Nippon Steel Works, “TEX-28 type twin screw extruder”). Melt kneaded. The strand discharged from the extruder was pelletized using a pelletizer (“SH type pelletizer” manufactured by Souken Co., Ltd.) to obtain a pellet-shaped thermoplastic resin composition.
The color developability, weather resistance, scratch resistance, and scratch resistance of the molded article of the obtained thermoplastic resin composition were evaluated as follows. The evaluation results are shown in Tables 6-8.

(Evaluation of color development)
From a pellet-shaped thermoplastic resin composition, using a 4-ounce injection molding machine manufactured by Nippon Steel Co., Ltd., cylinder setting temperature 260 ° C., mold temperature 80 ° C., injection rate 20 g / sec, length 100 mm, width A plate-shaped molded product having a thickness of 100 mm and a thickness of 3 mm was produced.
Subsequently, the determination index L ^* of the color of the molded product was measured using a colorimeter (CM-508d D65 10 ° SCE method manufactured by Minolta Co., Ltd.). The smaller L ^{*, the} better the color developability.

(Evaluation of weather resistance)
From a pellet-shaped thermoplastic resin composition, using a 4-ounce injection molding machine manufactured by Nippon Steel Co., Ltd., cylinder setting temperature 260 ° C., mold temperature 80 ° C., injection rate 20 g / sec, length 100 mm, width A plate-shaped molded product having a thickness of 100 mm and a thickness of 3 mm was produced.
Next, the surface of the obtained molded product was cut to a length of 70 mm and a width of 30 mm, and a super xenon weather meter (SX75AP manufactured by Suga Test Instruments Co., Ltd.) was used, in accordance with JIS D 0205 and JIS K 7350-2, 63 The test was conducted for 528 hours under the condition of ℃ and rain.
The degree of color change (ΔE) of the molded product before and after the test was measured using a colorimeter (CM-508d D65 10 ° SCE method manufactured by Minolta Co., Ltd.). The smaller ΔE, the better the weather resistance.

(Evaluation of scratch resistance)
From a pellet-shaped thermoplastic resin composition, using a 4-ounce injection molding machine manufactured by Nippon Steel Co., Ltd., cylinder setting temperature 260 ° C., mold temperature 80 ° C., injection rate 20 g / sec, length 100 mm, width A plate-shaped molded article (Ma) having a thickness of 100 mm and a thickness of 3 mm was produced, and the lightness L ^* of the surface was measured at an angle of 25 degrees using a goniocolorimeter. The L ^* measured in this way is referred to as “L ^* (ma)”.
As shown in FIG. 1, a rod-shaped jig 10 having a tip portion 11 formed in a square of 20 mm × 20 mm was prepared, and a mixed hand 12 was attached to the tip portion 11. The front end portion 11 to which the mixed spinning hand 12 is attached is brought into contact with the surface of the molded product (Ma) 13 so that the rod-shaped jig 10 is at a right angle. It was slid in the horizontal direction (arrow direction in the figure) and reciprocated 5 or 50 times. At that time, the applied load was 3.6 kg. After reciprocating 5 times or 50 times, the lightness L ^* of the surface of the scratched molded article (Mc) was measured at an angle of 25 degrees using a variable angle colorimeter. The L ^* measured in this way is referred to as “L ^* (mc)”.
(Determination of scratch resistance)
ΔL ^* was calculated from the following formula (2) as a determination index of the conspicuousness of scratches (scratches) on the molded product (Mc). As the absolute value of ΔL ^* is larger, the scratches are more conspicuous.
ΔL ^* = L ^* (mc) −L ^* (ma) (2)
The smaller the value of ΔL ^* calculated from Equation (2), the better the scratch resistance. Further, the [Delta] L ^* calculated from ^L * (mc) when the back and forth the tip 11 5 times in the above test, the [Delta] L ^* calculated from ^L * (mc) when the back and forth 50 times The smaller the difference, the better the scuff resistance.
This evaluation of scratch resistance can also be said to be evaluation of scratch resistance by a relatively soft material.

(Evaluation of scratch resistance)
The surface of the molded product (Ma) is scratched with a scratch tester (“Scratch Tester KK02” manufactured by Kato Tech Co., Ltd.) under the conditions of a load of 1 to 50 N, a pin shape of 1 mmφ, and a scratch rate of 100 mm / min. The value of the scratch friction coefficient SCOF at a load of 12N was read. Further, the lightness L ^* of the surface of the molded product (Me) with scratches was measured at an angle of 25 degrees using an angle-changing colorimeter. The L ^* measured in this way is referred to as “L ^* (me)”.
(Determination of scratch resistance)
ΔL ^* was calculated from the following formula (4) as a determination index of the conspicuousness of scratches (scratches) on the molded product (Me). As the absolute value of ΔL ^* is larger, the scratches are more conspicuous.
ΔL ^* = L ^* (me) −L ^* (ma) (4)
The smaller the value of ΔL ^* calculated from Equation (4), the better the scratch resistance.
Note that this evaluation of scratch resistance can also be said to be evaluation of scratch resistance with a relatively hard material.

The molded articles of the thermoplastic resin compositions of Examples 1 to 13 were all excellent in color developability, weather resistance, scratch resistance, and scratch resistance.
In Comparative Example 1, the density of the ethylene / α-olefin copolymer constituting the graft copolymer (E) is less than 0.870 g / cm ³ , and the molded article has scratch resistance, scratch resistance and weather resistance. Was low. In Comparative Example 2, the density of the ethylene / α-olefin copolymer constituting the graft copolymer (E) is more than 0.912 g / cm ³ , and the coloring property, scratch resistance, and scratch resistance of the molded product. And the weather resistance was low.
In Comparative Examples 3 to 5, the gel content of the ethylene / α-olefin copolymer constituting the graft copolymer (E) is more than 40% by mass, and the molded article has scratch resistance, scratch resistance and weather resistance. The sex was low.
Comparative Example 6 was a graft copolymer (F) in which the rubber polymer was only acrylic rubber, and the molded article had low scratch resistance, scratch resistance, and weather resistance.
In Comparative Example 7, the proportion of particles of 0.3 μm or more and 0.5 μm in the total particles of the composite rubber-like polymer is less than 5% by volume, and the molded article has scratch resistance, scratch resistance and weather resistance. It was low.
In Comparative Example 8, the volume average particle diameter of the composite rubber-like polymer is more than 0.2 μm, and the proportion of particles of 0.3 μm or more and 0.5 μm occupying in all particles is more than 25% by volume. , Scratch resistance, scratch resistance and weather resistance were low.
In Comparative Example 9, the volume average particle size of the composite rubber-like polymer is less than 0.1 μm, and the proportion of particles of 0.3 μm or more and 0.5 μm in the total particles is less than 5% by volume, and the scratch resistance of the molded product And scratch resistance were low.
In Comparative Example 10, the content of the graft copolymer (E) was less than 4% by mass, and the molded article had low scratch resistance, scratch resistance, and weather resistance.
In Comparative Example 11, the content ratio of the graft copolymer (E) was more than 10% by mass, and the weather resistance of the molded product was low.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which can manufacture easily the molded article which is excellent in all of coloring property, a weather resistance, an abrasion resistance, and a scratch resistance can be provided. In particular, the balance of color developability, weather resistance, scratch resistance, and scratch resistance of the thermoplastic resin composition of the present invention is higher than that of conventionally known thermoplastic resin compositions. A molded article of such a thermoplastic resin composition is suitable for vehicle exterior parts such as pillars, door mirrors, radiator grills, and spoilers, office equipment, home appliance parts, toys, stationery, miscellaneous goods, and the like, and is highly useful.

10 Jig 11 Tip 12 Blended Gun 13 Molded Product

Claims (2)

A thermoplastic resin composition comprising a graft copolymer (E), a graft copolymer (F), and a polymethacrylic acid ester (G),
The content ratio of the graft copolymer (E) is 4% by mass to 15% by mass with respect to 100% by mass of the thermoplastic resin composition,
The graft copolymer (E) is a vinyl monomer mixture (m1) containing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of the ethylene / α-olefin copolymer (a). ) Is a copolymer obtained by graft polymerization,
The graft copolymer (F) is one or more kinds in the presence of a composite rubber-like polymer (d) in which a polyorganosiloxane (b) and an alkyl (meth) acrylate polymer (c) are combined. A copolymer obtained by graft polymerization of a vinyl monomer (m2),
The ethylene · alpha-olefin copolymer (a) has a density less than 0.870 g / cm ³ or more 0.912 g / cm ^3, a volume average particle diameter is at 0.2μm or 0.4μm or less, the gel The content is 3% by mass or less,
The composite rubber-like polymer (d) has a volume average particle size of 0.1 μm or more and 0.2 μm or less, and a particle size of 0.3 μm or more occupied in all the particles of the composite rubber-like polymer (d). A thermoplastic resin composition, wherein the proportion of particles of 0.5 μm or less is 5% by volume or more and 25% by volume or less.   A molded article containing the thermoplastic resin composition according to claim 1.

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