JP2020019942A - Thermoplastic resin composition, resin molding, vehicular exterior member, and vehicular interior member - Google Patents

Abstract

To provide a thermoplastic resin composition excellent in scratch resistance and impact resistance.SOLUTION: The thermoplastic resin composition contains a (meth)acrylic polymer (A), a fatty acid amide (B), and multilayer-structured graft copolymer particles (C). The fatty acid amide (B) is at least one selected from stearic acid amide and palmitic acid amide. The multilayer-structured graft copolymer particles (C) are a multilayer-structured graft copolymer having: a rubbery copolymer (C1) having a crosslinked structure; and an outer layer polymer (C2) obtained by polymerizing a monomer mixture containing an alkyl acrylate (C2-1) having a C1-8 alkyl group as an ester side chain and an alkyl methacrylate (C2-2) having a C1-8 alkyl group as an ester side chain in the presence of the rubbery copolymer (C1).SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition having excellent scratch resistance, friction wear resistance and impact resistance, a resin molded article containing the thermoplastic resin composition, a vehicle exterior member including the resin molding, and a vehicle. It relates to an interior member.

  (Meth) acrylic resins are materials for housing equipment such as vanities, bathtubs, flush toilets, etc .; building materials; vehicle materials such as vehicle interior / exterior materials because of their excellent appearance, dimensional stability and chemical resistance. , Is widely used in many applications.

  Recently, particularly, (meth) acrylic resins are used for vehicles such as pillar covers, lamp covers, mirror covers, visors, front protectors, front grills, garnishes, rear spoilers, rear grills, and emblems (hereinafter, referred to as "pillar covers"). Use for exterior materials for vehicles, interior materials for vehicles such as instrument covers and meter panels, as well as materials for housing equipment such as decorative sheets used for edge bands of furniture and fixtures, housing for home appliances, lighting The use of the cover of equipment, sanitary goods, the front panel or display window of an elastic game machine, the cover of an LED light source or a lamp light source (hereinafter, referred to as “use of home appliances and housing materials”) is being studied. .

  When the (meth) acrylic resin is used for an interior member for a vehicle, an application for a home appliance and a house building material and the like, particularly for an exterior member for a vehicle such as the pillar cover, the (meth) acrylic resin may be used with a person or an object during use of the product. In the case of contact or in an automatic car washer, the product may be scratched due to high-speed rotation of a rotating plastic car wash brush made of a plastic such as polypropylene resin or polyethylene resin. There is a demand for (meth) acrylic resins having excellent wear properties.

  In addition, when the (meth) acrylic resin is used for an interior member for a vehicle, an exterior member for a vehicle such as a pillar cover, an appliance such as a home appliance and a house building material, the product may be dropped or may not be used. The impact may be applied to the product due to contact or contact with a person or an object while the vehicle is running, and the product may be damaged. Therefore, a (meth) acrylic resin having excellent impact resistance is required.

  As a method for improving the impact resistance, abrasion resistance, and abrasion resistance of a (meth) acrylic resin, for example, Patent Document 1 discloses an acrylic resin composition containing an impact resistance improving agent and a siloxane compound. I have. Patent Document 2 discloses an acrylic resin composition in which a surface property improving agent containing a rubber, an ethylene / vinyl copolymer, a fatty acid amide, and a graft copolymer is blended.

JP 2013-504680 A JP-A-2013-131948

The acrylic resin composition disclosed in Patent Literature 1 does not have sufficient surface slipperiness of a molded article, and the obtained resin molded article is inferior in scratch resistance and abrasion resistance.
The acrylic resin composition disclosed in Patent Document 2 is insufficient in abrasion resistance and abrasion resistance. In addition, since the material constituting the surface property improving agent is contained in a large amount, the obtained resin molded article is inferior in impact resistance and the transparency characteristic of the acrylic resin is impaired.

  Therefore, an object of the present invention is to provide a thermoplastic resin composition having excellent scratch resistance, friction and wear resistance, and impact resistance.

The above object is achieved by the present invention described below.
A first gist of the present invention is a thermoplastic resin composition comprising a (meth) acrylic polymer (A), a fatty acid amide (B), and a multilayer graft copolymer particle (C), wherein the fatty acid amide ( B) is at least one member selected from stearic acid amide and palmitic acid amide, and the multilayer structure graft copolymer particles (C) are composed of a rubbery copolymer (C1) having a crosslinked structure and the rubbery copolymer (C1). In the presence of the union (C1), an alkyl acrylate (C2-1) having an alkyl group having 1 to 8 carbon atoms as an ester side chain, an alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms as an ester side chain ( The thermoplastic resin composition is a fine particle of a multilayer graft copolymer having an outer layer polymer (C2) obtained by polymerizing a monomer mixture containing C2-2).
A second gist of the present invention resides in a resin molded article containing the thermoplastic resin composition.
A third aspect of the present invention resides in a vehicle exterior member including the resin molded body.
A fourth aspect of the present invention resides in a vehicle interior member including the resin molded body.
The fifth gist of the present invention is selected from the group consisting of materials for housing equipment, housing of home electric appliances, covers of lighting equipment, sanitary goods, front panels or display windows of elastic game machines, covers of LED light sources or lamp light sources. The resin molded article used in any of the above.

According to the present invention, it is possible to stably provide a thermoplastic resin composition having excellent scratch resistance, friction wear resistance and impact resistance.
The thermoplastic resin composition of the present invention is used for exterior members for vehicles such as pillar covers, used for exterior members for vehicles such as instrument covers and meter panels, and further used for decorative sheets used for edge bands of furniture and fixtures. It is suitable for use in such materials for housing equipment, housing for home appliances, covers for lighting equipment, sanitary supplies, front panels or display windows of elastic game machines, and covers for LED light sources or lamp light sources.

It is a schematic diagram explaining the outline | summary of the scratch resistance test used for evaluation of the molded object of this invention. The arrow in the figure indicates the MD direction (flow direction during molding) from the gate position during injection molding in the example.

Hereinafter, the present invention will be described in detail.
In the present invention, “(meth) acrylate” means at least one selected from “acrylate” and “methacrylate”, and “(meth) acrylic acid” is selected from “acrylic acid” and “methacrylic acid” It means at least one kind.
In the present invention, “monomer” means an unpolymerized compound, and “repeat unit” means a unit derived from the monomer and formed by polymerization of the monomer. The repeating unit may be a unit directly formed by a polymerization reaction, or a unit in which a part of the unit is converted to another structure by treating a polymer.
In the present invention, “% by mass” indicates a content ratio of a specific component contained in the total amount of 100% by mass.
Unless otherwise specified, a numerical range represented by using “to” in the present specification means a range including the numerical values described before and after “to” as a lower limit and an upper limit, and “A to B” Means not less than A and not more than B.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention is a resin composition containing a (meth) acrylic polymer (A) described later, a fatty acid amide (B) described later, and a multilayer graft copolymer particle (C) described later. .
By containing the (meth) acrylic polymer (A), the (meth) acrylic resin composition of the present invention and a resin molded product obtained by molding the (meth) acrylic resin composition of the present invention (hereinafter simply referred to as “ Transparency, weather resistance, and moldability of the obtained “resin molded article” are improved.
By containing the fatty acid amide (B), the resulting resin molded article has good scratch resistance and friction and wear resistance.
By including the multilayer structure graft copolymer particles (C), the impact resistance of the obtained resin molded article is improved.

Further, in the thermoplastic resin composition of the present invention, from the viewpoint that the impact resistance of the obtained resin molded product is further improved, the fatty acid amide (B) is changed to the glass transition temperature of the (meth) acrylic polymer (A). It is preferable that the difference between T1 (unit: ° C) and the melting point T2 (unit: ° C) of the fatty acid amide (B) satisfies the following general formula (1).
| T1-T2 | ≦ 10 (1)

When the resin composition containing the acrylic polymer (A) and the fatty acid amide (B) was molded using a known molding means such as an injection molding method or an extrusion molding method, the resin composition was uniformly compatible at a high temperature. As the value of | T1−T2 | of the molten mixture of the acrylic polymer (A) and the fatty acid amide (B) increases, the fatty acid amide (B) aggregates in the resin molded body during the cooling process, or Since the fatty acid amide (B) tends to bleed out from the resin molded product, the resulting resin molded product has reduced abrasion resistance and abrasion resistance. However, as shown in the above formula (1), when the value of | T1-T2 | is 10 or less, molding is performed in a state where the (meth) acrylic polymer (A) and the fatty acid amide (B) are uniformly dispersed. Since the fatty acid amide (B) is uniformly dispersed on the surface of the obtained resin molded product, the obtained resin molded product has good scratch resistance and friction wear. The value of | T1-T2 | is more preferably 6 or less, and still more preferably 4 or less.
The details of the method for measuring the glass transition temperature and the melting point will be described later.

<(Meth) acrylic polymer (A)>
The (meth) acrylic polymer (A) is one of the constituent components of the thermoplastic resin composition of the present invention.
By containing the (meth) acrylic polymer (A), the thermoplastic resin composition of the present invention improves the transparency of the obtained resin molded product, suppresses the thermal decomposition of the resin molded product, and improves the weather resistance. Properties and moldability can be improved.

  As the (meth) acrylic polymer (A) of the present invention, a repeating unit derived from methyl methacrylate (hereinafter, referred to as “MMA unit”) is 80 based on 100% by mass of the total mass of the (meth) acrylic polymer (A). A methyl methacrylate copolymer containing not less than 100% by mass and less than 100% by mass or a homopolymer of methyl methacrylate can be used.

From the viewpoint of improving the mechanical strength or the thermal decomposition resistance of the obtained resin molded product, the (meth) acrylic polymer (A) contains 80% by mass or more and less than 100% by mass of an MMA unit and an alkyl having 2 to 8 carbon atoms. A repeating unit derived from an alkyl (meth) acrylate (M) containing a group as an ester side chain (hereinafter referred to as “alkyl (meth) acrylate (M) unit”) containing more than 0% by mass and not more than 20% by mass. A copolymer containing 80% by mass or more and 99.5% by mass or less of MMA units and 0.5% by mass or more and 20% by mass or less of alkyl (meth) acrylate (M) units is more preferable, and 90% by mass of MMA units. A copolymer containing at least 98% by mass and not more than 2% by mass and at most 10% by mass of an alkyl (meth) acrylate (M) unit is more preferable.
Alternatively, the (meth) acrylic polymer (A) may be a homopolymer of MMA from the viewpoint of improving the transparency, heat resistance and weather resistance of the obtained resin molded article.

The alkyl (meth) acrylate (M) is not particularly limited as long as it is a monomer copolymerizable with methyl methacrylate, and examples thereof include the following a) to h).
a) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate Tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate , Stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate Tetrahydrofurfuryl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexanedimethanol mono (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, Toxiethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 2- (meth) acryloyloxymethyl-2-methylbicycloheptane, 4- (meth) acryloyloxymethyl-2- (Meth) acrylate compounds other than methyl methacrylate, such as methyl-2-ethyl-1,3-dioxolan, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolan;
b) (meth) acrylic acid;
c) (meth) acrylonitrile;
d) (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-butyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxy (Meth) acrylamide compounds such as methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, and methylenebis (meth) acrylamide;
e) aromatic vinyl compounds such as styrene and α-methylstyrene;
f) vinyl ether compounds such as vinyl methyl ether, vinyl ethyl ether and 2-hydroxyethyl vinyl ether;
g) vinyl carboxylate compounds such as vinyl acetate and vinyl butyrate;
h) Olefin compounds such as ethylene, propylene, butene and isobutene.
One of these alkyl (meth) acrylates (M) may be used alone, or two or more thereof may be used in combination.
Among the alkyl (meth) acrylates (M), (meth) acrylate compounds other than methyl methacrylate are preferable because they do not easily impair the inherent performance of the (meth) acrylic resin. Methyl acrylate, ethyl acrylate, and n-butyl acrylate are more preferable, and methyl acrylate and ethyl acrylate are more preferable, since the properties and heat moldability are improved.

  Examples of the method for producing the (meth) acrylic polymer (A) include a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. Among these polymerization methods, from the viewpoint of excellent productivity, the (meth) acrylic polymer (A) is preferably produced by a bulk polymerization method or a suspension polymerization method, and more preferably produced by a bulk polymerization method. preferable.

The mass average molecular weight of the (meth) acrylic polymer (A) is preferably from 20,000 to 200,000, more preferably from 50,000 to 150,000.
When the mass average molecular weight of the (meth) acrylic polymer (A) is equal to or more than the lower limit, the obtained resin molded article tends to have excellent mechanical properties. Tends to be excellent. The lower limit of the mass average molecular weight of the (meth) acrylic polymer (A) is more preferably 50,000. The upper limit of the weight average molecular weight of the (meth) acrylic polymer (A) is more preferably 150,000.

  In the present specification, the mass average molecular weight is a value measured by using gel permeation chromatography using standard polystyrene as a standard sample.

The lower limit of the content ratio of the (meth) acrylic polymer (A) contained in the total mass (100 mass%) of the thermoplastic resin composition of the present invention is not particularly limited. preferable. 70 mass% is more preferable, and 90 mass% is still more preferable. On the other hand, the upper limit of the content ratio of the (meth) acrylic polymer (A) is not particularly limited, and is preferably 99% by mass or less. 98 mass% is more preferable, and 97 mass% is further more preferable.
Alternatively, the content of the (meth) acrylic polymer (A) in the total mass (100 mass%) of the thermoplastic resin composition of the present invention is preferably from 55 mass% to 99 mass%, more preferably 70 mass%. The content is more preferably at least 98% by mass and more preferably at least 90% by mass and at most 97% by mass.
If the content of the (meth) acrylic polymer (A) in the total mass (100% by mass) of the thermoplastic resin composition of the present invention is equal to or more than the lower limit, the obtained resin molded product has transparency. In addition, the inherent performance of the acrylic resin such as heat resistance and weather resistance is not easily impaired, and if it is not more than the above upper limit, the obtained resin molded article tends to have excellent scratch resistance.

<Fatty acid amide (B)>
Fatty acid amide (B) is one of the constituent components of the thermoplastic resin composition of the present invention.
In the thermoplastic resin composition of the present invention, the fatty acid amide (B) includes a fatty acid group and an amide group in the molecule from the viewpoint that the obtained resin molded article can have excellent scratch resistance and friction and wear resistance. And a compound containing at least one selected from stearic acid amide and palmitic acid amide.

  In the thermoplastic resin composition of the present invention, the fatty acid amide (B) is used in the thermoplastic resin composition of the present invention in view of improving the scratch resistance and the friction and abrasion resistance of the obtained resin molded article. It is preferable that at least one selected from stearamide and palmitamide is contained in a total content of at least 80% by mass, more preferably at least 90% by mass, and at least 95% by mass with respect to the mass%. Is more preferred.

  Further, in the thermoplastic resin composition of the present invention, from the viewpoint that the resulting resin molded article has better scratch resistance and friction and wear resistance, the fatty acid amide (B) is replaced with stearic acid amide and the fatty acid amide. The content of (B) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more based on the total mass of 100% by mass.

When the number of carbon atoms of the fatty acid amide (B) is smaller than the number of carbon atoms of the stearic acid amide and the palmitic acid amide, the fatty acid amide tends to bleed out. At the same time, the scratch resistance tends to decrease. On the other hand, when the number of carbon atoms of the fatty acid amide (B) is larger than the number of carbon atoms of the stearic acid amide and the palmitic acid amide, the compatibility between the (meth) acrylic resin (A) and the fatty acid amide is reduced. The body's scratch resistance tends to decrease.
Furthermore, in the thermoplastic resin composition of the present invention, by using the fatty acid amide (B) and the multilayer graft copolymer particles (C) in combination, the multilayer graft copolymer particles (C) are contained in the thermoplastic resin composition. It is presumed that C) is more uniformly dispersed, so that the impact resistance of the obtained resin molded product becomes better. Further, the interaction between the (meth) acrylic resin (A), the fatty acid amide (B) and the multilayer graft copolymer particles (C) reduces the friction coefficient of the surface of the obtained resin molded product. In addition, the elasticity of the thermoplastic resin composition is increased, and when the obtained resin molded body comes into contact with an impact object, the surface of the obtained resin molded body is plastically deformed or the contacted portion is damaged. It is presumed that the resulting resin molded article would have better scratch resistance and abrasion resistance because it becomes more difficult to perform.

The lower limit of the content ratio of the fatty acid amide (B) contained in the thermoplastic resin composition of the present invention is from the viewpoint of excellent abrasion resistance and abrasion resistance of the obtained resin molded product. Is preferably 0.9% by mass, more preferably 1.2% by mass, even more preferably 1.4% by mass, based on 100% by mass of the total The upper limit of the content ratio of the fatty acid amide (B) is preferably 4.0% by mass with respect to the total mass of 100% by mass of the thermoplastic resin composition, from the viewpoint of not impairing the inherent performance of the (meth) acrylic resin. 3.0 mass% is more preferable, and 2.5 mass% is still more preferable. The above upper and lower limits can be arbitrarily combined.
Alternatively, the content ratio of the fatty acid amide (B) contained in the thermoplastic resin composition of the present invention is preferably from 0.9% by mass to 4.0% by mass, and more preferably from 1.2% by mass to 3.0% by mass. % Or less, more preferably 1.4% by mass or more and 2.5% by mass or less.

  Examples of the fatty acid amide (B) include, for example, Steramide manufactured by Tokyo Chemical Industry Co., Ltd., IncroMaxPS manufactured by CRODA, Amid S manufactured by Kao Corporation, Amid AP-1 manufactured by Mitsubishi Chemical Corporation, Diamond 200, and Diamond Mid. Commercial products such as KP can be used.

<Multilayer Graft Copolymer Particle (C)>
The multilayer graft copolymer particles (C) are one of the constituent components of the thermoplastic resin composition of the present invention.
When the thermoplastic resin composition of the present invention contains the multilayer structure graft copolymer particles (C), the obtained resin molded article has excellent impact resistance.

The multilayer-structured graft copolymer particles (C) of the present invention have excellent compatibility with the (meth) acrylic polymer (A), and from the viewpoint of excellent impact resistance of the obtained resin molded article, the rubber elastic layer Fine particles containing an inner layer and an outer layer that is a hard layer are preferable.
As the multilayer graft copolymer particles (C) of the present invention, specifically, a rubbery copolymer (C1) having a crosslinked structure and a carbon number in the presence of the rubbery copolymer (C1) A monomer mixture containing an alkyl acrylate (C2-1) having 1 to 8 or less alkyl groups as an ester side chain, and an alkyl methacrylate (C2-2) having an alkyl group having 1 to 8 carbon atoms or less as an ester side chain. It is a multilayer graft copolymer having an outer layer polymer (C2) obtained by polymerization.
That is, in the multilayer graft copolymer, the inner layer, which is a rubber elastic layer, is composed of the rubbery copolymer (C1), and the outer layer, which is a hard layer, is composed of the outer layer polymer (C2). .

  When the multilayer structure graft copolymer particles (C) contain the rubbery copolymer (C1) having a crosslinked structure, the thermoplastic resin composition of the present invention has good impact resistance.

  The multilayer structure graft copolymer particles (C) contain the outer layer polymer (C2) in the outer layer of the rubbery copolymer (C1), that is, the outermost layer of the multilayer structure graft copolymer particles (C). Interacts with the fatty acid amide (B) and uniformly disperses in the thermoplastic resin composition, so that the thermoplastic resin composition of the present invention has scratch resistance, abrasion resistance, impact resistance, and transparency. Is good.

  The multilayer-structured graft copolymer particles (C) are obtained by multiplying a repeating unit derived from one or more monomers of alkyl methacrylate, alkyl acrylate, aromatic vinyl compound, acrylonitrile, methacrylonitrile, or butadiene. It is preferable to contain 5% by mass or more, especially 10% by mass or more, based on the total mass (100% by mass) of the copolymer particles (C).

  In particular, for applications requiring a high degree of transparency and weather resistance, the multilayer graft copolymer particles (C) are derived from at least one monomer selected from alkyl methacrylates, alkyl acrylates and aromatic vinyl compounds. The total amount of the repeating units is preferably 10% by mass or more, more preferably 12% by mass or more, based on the total mass (100% by mass) of the multilayer graft copolymer particles (C).

  The method of qualitatively and quantitatively determining the structure of the structural unit derived from the monomer constituting the multilayer graft copolymer particles (C) is not particularly limited. For example, when the thermoplastic resin composition of the present invention is dissolved in a soluble solvent and the multilayered graft copolymer particles (C) are dissolved, the multilayered graft copolymer particles (C) are obtained by preparative chromatography. After fractionation of C), it can be qualitatively and quantitatively determined using a known analysis method such as nuclear magnetic resonance spectroscopy. Alternatively, when the multi-layered graft copolymer particles (C) do not dissolve, the multi-layered graft copolymer particles (C) are collected by filtration and then subjected to a pyrolysis gasgram method, a pyrolysis nuclear magnetic resonance spectroscopy method, or the like. Can be qualitatively and quantitatively determined using the known analysis method described in

<Rubber-like copolymer having cross-linked structure (C1)>
The rubber-like copolymer (C1) having a crosslinked structure is one of the constituent components of the multilayer graft copolymer particles (C) of the present invention, and is a polymer constituting an inner layer that is a rubber elastic layer.
The rubbery copolymer (C1) is a repeating unit (hereinafter, referred to as “alkyl acrylate (C1-1)”) derived from an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms as an ester side chain (hereinafter, referred to as “alkyl acrylate (C1-1)”). Acrylate (C1-1) unit ").).
The lower limit of the glass transition temperature of the homopolymer of the alkyl acrylate (C1-1) is preferably −80 ° C., more preferably −60 ° C., from the viewpoint of excellent productivity of the thermoplastic resin composition of the present invention. On the other hand, the upper limit of the glass transition temperature of the homopolymer of the alkyl acrylate (C1-1) is preferably 25 ° C., more preferably 10 ° C., from the viewpoint of excellent low-temperature impact resistance of the obtained resin molded product. .
Alternatively, the glass transition temperature of the homopolymer of the alkyl acrylate (C1-1) is preferably from -80C to 25C, more preferably from -60C to 10C. The glass transition temperature is a value measured by heat flux differential scanning calorimetry in accordance with ISO 3146.

  The content ratio of the monomer units constituting the rubber-like copolymer (C1) is determined based on the total mass (100% by mass) of the rubber-like copolymer (C1) from the viewpoint of excellent impact resistance of the obtained resin molded product. ), An alkyl acrylate (C1-1) unit of 40% by mass to 88.9% by mass, a repeating unit derived from a non-crosslinkable monomer (C1-2) other than the alkyl acrylate (C1-1) (hereinafter, referred to as " 10% by mass to 58.9% by mass of a structural unit derived from the crosslinkable monomer (C1-3) (hereinafter referred to as "crosslinkable monomer (C1-2) unit"). (Referred to as “(C1-3) unit”). It is preferable that the amount is 0% by mass to 10% by mass, and the graft-linking agent (C1-4) is 0.1% by mass to 10% by mass. Furthermore, alkyl acrylate (C1-1) unit 60 mass%-84.8 mass%, non-crosslinkable monomer (C1-2) unit 15 mass%-38.8 mass%, crosslinkable monomer (C1- 3) It is more preferable that the amount is from 0% by mass to 5% by mass and the graft-linking agent (C1-4) is from 0.2% by mass to 5% by mass.

Examples of the alkyl acrylate (C1-1) include ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, Cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxy Ethyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-h B carboxybutyl acrylate. One of these monomers may be used alone, or two or more thereof may be used in combination.
Among these alkyl acrylates (C1-1), ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate are preferred from the viewpoint of excellent impact resistance of the obtained resin molded article. Preferably, n-butyl acrylate is more preferable.

Examples of the non-crosslinkable monomer (C1-2) include methyl (meth) acrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) ) Acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 2- (meth) acryloyloxymethyl-2- Methylbicycloheptane, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolan, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxo (Meth) acrylate compounds other than alkyl acrylates having 2 to 8 carbon atoms such as butane; (meth) acrylic acid; (meth) acrylonitrile; (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide N-butyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, (Meth) acrylamide compounds such as methylenebis (meth) acrylamide; aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl such as vinyl methyl ether, vinyl ethyl ether and 2-hydroxyethyl vinyl ether Ether compounds; vinyl acetate, vinyl carboxylate compounds such as vinyl butyrate, ethylene, propylene, butene, olefinic compounds such isobutene and the like.
One of these monomers may be used alone, or two or more thereof may be used in combination.
Among these non-crosslinkable monomers (C1-2), (meth) acrylate compounds other than alkyl acrylate (C1-1) and aromatic vinyl compounds are preferable from the viewpoint of excellent appearance of the obtained resin molded article. , Methyl methacrylate and styrene are more preferred.

The crosslinkable monomer (C1-3) is a monomer having a plurality of polymerizable double bonds having the same reactivity, for example, 1,3-butylene (meth) acrylate, 1,4-butane And diol di (meth) acrylate. One of these monomers may be used alone, or two or more thereof may be used in combination.
Among these crosslinkable monomers (C1-3), from the viewpoint of excellent copolymerizability with alkyl acrylates having 2 to 8 carbon atoms, 1,3-butylene (meth) acrylate and 1,4-butanediol (Meth) acrylate is preferred, and 1,3-butylene di (meth) acrylate is more preferred.

The graft crossing agent (C1-4) is a monomer having a plurality of polymerizable double bonds having different reactivities, and examples thereof include allyl (meth) acrylate. One of these grafting agents may be used alone, or two or more thereof may be used in combination.
Among these graft crosslinking agents (C1-4), allyl (meth) acrylate is preferred, and allyl methacrylate is more preferred, from the viewpoint of excellent copolymerizability with the alkyl acrylate (C1-1).

  The rubbery copolymer (C1) may be a single layer or a multilayer, but from the viewpoint of excellent productivity, preferably 1 to 3 layers, more preferably 1 or 2 layers.

<Outer layer polymer (C2)>
The outer layer polymer (C2) is one of the constituents of the multilayer graft copolymer particles (C) of the present invention, and is a polymer constituting the outer layer that is a hard layer.

The outer layer polymer (C2) is preferably made of a material having a glass transition temperature.
The lower limit of the glass transition temperature of the outer layer polymer (C2) is preferably 60 ° C from the viewpoint of excellent appearance of the obtained resin molded article. The upper limit of the glass transition temperature of the outer layer polymer (C2) is preferably 150 ° C. from the viewpoint of excellent impact resistance of the obtained resin molded article.
Alternatively, the glass transition temperature of the outer layer polymer (C2) is preferably from 50 to 200C, more preferably from 60 to 150C.

The outer layer polymer (C2) is a repeating unit (hereinafter, referred to as “alkyl acrylate”) derived from an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms as an ester side chain (hereinafter, referred to as “alkyl acrylate (C2-1)”). (Hereinafter referred to as "C2-1) unit") and a repeating unit (hereinafter referred to as "alkyl methacrylate (C2-2)") having an alkyl group having 1 to 8 carbon atoms as an ester side chain (hereinafter referred to as "alkyl methacrylate (C2-2)"). , "Alkyl methacrylate (C2-2) units").

As the outer layer polymer (C2), from the viewpoint of excellent appearance of the obtained resin molded article, the alkyl acrylate (C2-1) unit is based on the total mass (100% by mass) of the outer layer polymer (C2). Copolymers containing more than 0% by mass and 50% by mass or less and 50% by mass or more and less than 100% by mass of alkyl methacrylate (C2-2) units can be exemplified.
Further, the outer layer polymer (C2) is an alkyl (meth) acrylate other than the alkyl acrylate (C2-1) and the alkyl methacrylate (C2-2) as long as the performance of the thermoplastic resin composition of the present invention is not impaired. , "Other alkyl (meth) acrylate (C2-3)") (hereinafter, referred to as "other alkyl (meth) acrylate (C2-3) unit").

As the alkyl acrylate (C2-1), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n- Hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl Acrylate, 4-hydroxybutyl acrylate. One of these monomers may be used alone, or two or more thereof may be used in combination.
Among these alkyl acrylates (C2-1), methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferred, and methyl acrylate is more preferred, from the viewpoint of improving the thermal stability of the multilayer graft copolymer particles (C). preferable.

As the alkyl methacrylate (C2-2), for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n- Hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-hydroxy Butyl methacrylate, 3-hydroxybutyrate methacrylate le, 4-hydroxybutyl methacrylate and the like. One of these monomers may be used alone, or two or more thereof may be used in combination.
Among these alkyl methacrylates (C2-2), methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate are preferable, and methyl methacrylate is more preferable, from the viewpoint of excellent transparency of the obtained resin molded product.

  The other alkyl (meth) acrylate (C2-3) is not particularly limited as long as it is a monomer copolymerizable with the alkyl acrylate (C2-1) and the alkyl methacrylate (C2-2). For example, (meth) acrylate compounds such as dodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; (meth) acrylic acid; aromatic vinyl such as styrene and α-methylstyrene Compounds; Vinyl ether compounds such as vinyl methyl ether, vinyl ethyl ether and 2-hydroxyethyl vinyl ether; vinyl carboxylate compounds such as vinyl acetate and vinyl butyrate; (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) ) Acrylamide, -Butyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, methylenebis ( (Meth) acrylamide compounds such as (meth) acrylamide; vinyl cyanide compounds such as (meth) acrylonitrile; and olefin compounds such as ethylene, propylene, butene, and isobutene. One of these monomers may be used alone, or two or more thereof may be used in combination.

  The outer layer may be a single layer or a multilayer, but is preferably 1 to 3 layers, more preferably 1 or 2 layers, because of excellent productivity.

The mass ratio of the inner layer to the outer layer is preferably 20% by mass to 80% by mass of the inner layer and 20% by mass to 80% by mass of the outer layer with respect to the total mass (100% by mass) of the multilayer graft copolymer particles (C). More preferably, the inner layer is 50% by mass to 70% by mass, and the outer layer is 30% by mass to 50% by mass.
When the proportion of the mass of the inner layer is equal to or more than the lower limit value and the proportion of the mass of the outer layer is equal to or less than the upper limit value, the total mass (100 mass%) of the multilayer graft copolymer particles (C) is obtained. When the resin composition has a tendency to be excellent in impact resistance, the ratio of the mass of the inner layer is equal to or less than the upper limit, and the ratio of the mass of the outer layer is equal to or greater than the lower limit, the multilayer structure graft copolymer particles (C ) And (meth) acrylic polymer (A) tend to be excellent in compatibility.

  As a method for producing the multilayer structure graft copolymer particles (C), a known method can be employed, and examples thereof include a suspension polymerization method and an emulsion polymerization method. Among them, the emulsion polymerization method is preferred from the viewpoint of excellent productivity.

As the emulsifier used in the emulsion polymerization, a known emulsifier can be adopted, for example, sodium mono-n-dodecyloxytetraoxyethylene phosphate (hereinafter, also referred to as “emulsifier E”),
Sodium di-n-dodecyloxytetraoxyethylene phosphate (hereinafter also referred to as "emulsifier F"),
A 1: 1 (mass ratio) mixture of emulsifier E and emulsifier F (hereinafter also referred to as "emulsifier G");
A mixture of emulsifier E, emulsifier F and dodecyloxytrioxyethyleneoxyethanol in a ratio of 1: 1: 0.2 (mass ratio) (hereinafter, also referred to as “emulsifier H”);
Sodium mono-n-dodecyloxyhexaoxyethylene phosphate (hereinafter also referred to as "emulsifier I"),
Sodium di-n-dodecyloxyhexaoxyethylene phosphate (hereinafter also referred to as "emulsifier J"),
A mixture of emulsifier I, emulsifier J and dodecyloxypentaoxyethyleneoxyethanol in a ratio of 1: 0.3: 0.3 (mass ratio) (hereinafter also referred to as "emulsifier K");
Sodium mono-isotridecyloxyhexaoxyethylene phosphate (hereinafter also referred to as "emulsifier L"),
Sodium di-isotridecyloxyhexaoxyethylene phosphate (hereinafter also referred to as “emulsifier M”),
A mixture of emulsifier L, emulsifier M and isotridecyloxypentaoxyethyleneoxyethanol in a ratio of 1: 1: 0.2 (mass ratio) (hereinafter, also referred to as “emulsifier N”);
A mixture of emulsifier L, emulsifier M and isotridecyloxypentaoxyethyleneoxyethanol in a ratio of 1: 1: 0.1 (mass ratio) (hereinafter also referred to as “emulsifier O”);
A mixture of emulsifier L, emulsifier M and isotridecyloxypentaoxyethyleneoxyethanol in a ratio of 1: 1.5: 0.05 (mass ratio) (hereinafter also referred to as “emulsifier P”);
A mixture of emulsifier L, emulsifier M and isotridecyloxypentaoxyethyleneoxyethanol in a ratio of 1: 0.4: 0.4 (mass ratio) (hereinafter also referred to as “emulsifier Q”);
A mixture of potassium mono-n-dodecyloxypentaoxyethylene phosphate, potassium di-n-dodecyloxypentaoxyethylene phosphate and n-dodecyloxytetraoxyethyleneoxyethanol at a ratio of 1: 3: 1 (mass ratio)) , "Emulsifier R").

  Examples of a method for adding a monomer or the like in the emulsion polymerization include a batch addition method, a divided addition method, and a continuous addition method. One of these addition methods may be used alone, or two or more may be used in combination. Among them, the split addition method is preferred from the viewpoint of excellent quality of the impact resistance improver.

The mass average particle diameter of the multilayer graft copolymer particles (C) is preferably from 10 nm to 1000 nm, more preferably from 50 nm to 500 nm. When the mass average particle diameter of the multilayer structure graft copolymer particles (C) is at least the lower limit, the resulting resin molded article tends to have excellent impact resistance. The resin molded body tends to have excellent chemical resistance.
In addition, in this specification, the mass average particle diameter is a value measured by capillary hydrodynamic flow fractionation.

  A known method can be used as a method of powdering the multilayer structure graft copolymer particles (C), and examples thereof include a coagulation method and a spray drying method. Among them, the coagulation method is preferred from the viewpoint of excellent quality of the impact resistance improver.

The upper limit of the content of the multilayer graft copolymer particles (C) contained in the thermoplastic resin composition of the present invention is (meta) with respect to the total mass (100 mass%) of the thermoplastic resin composition. From the viewpoint that the inherent performance of the acrylic resin is not easily impaired, 40% by mass is preferable, and 30% by mass is more preferable. On the other hand, the lower limit of the content of the multilayer graft copolymer particles (C) is preferably 1% by mass, more preferably 10% by mass, from the viewpoint of excellent impact resistance of the obtained resin molded article.
Alternatively, the content ratio of the multilayer structure graft copolymer particles (C) contained in the thermoplastic resin composition of the present invention is 1% by mass relative to the total mass (100% by mass) of the thermoplastic resin composition. % To 10% by mass, more preferably 10% to 30% by mass.

<Other additives>
The thermoplastic resin composition of the present invention is a known release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, as long as the performance of the obtained resin molded article is not impaired. It can contain various additives such as a flame retardant, a flame retardant auxiliary, a polymerization inhibitor, a filler, a pigment, a dye, a silane coupling agent, a leveling agent, a defoaming agent, a fluorescent agent, and a chain transfer agent. One of these other additives may be used alone, or two or more thereof may be used in combination.

Furthermore, the thermoplastic resin composition of the present invention contains carbon black or a dye as another additive, so that the molded article obtained by molding the thermoplastic resin composition of the present invention has a deep jet blackness. Can be expressed.
The type of carbon black is not particularly limited, and known carbon black can be used.
The type of the dye is not particularly limited, and a known dye can be used. For example, three or more dyes selected from the group consisting of red dyes, yellow dyes, green dyes, blue dyes, and violet dyes can be used in combination.

Furthermore, the thermoplastic resin composition of the present invention can express deeper jet-blackness in a molded article obtained by molding the thermoplastic resin of the present invention by including carbon black and a dye together.
The content ratio of the other additives contained in the thermoplastic resin composition of the present invention is 0% by mass or more and 20% by mass or less based on the total mass (100% by mass) of the thermoplastic resin composition. Can be.
Further, the thermoplastic resin composition of the present invention may contain a silicone compound containing at least one selected from dimethyl silicone and polyester-modified silicone as a lubricant. By including the silicone compound in combination with the fatty acid amide (B), the effect of improving the scratch resistance and the friction and abrasion resistance of both compounds can be obtained without increasing the content of the fatty acid amide (B). Since the scratch resistance and abrasion resistance of the obtained resin molded article can be further improved, the inherent performance of the (meth) acrylic resin such as transparency, heat resistance and weather resistance is not easily impaired.

  Furthermore, by using the fatty acid amide (B) and the silicone compound together, the multilayer graft copolymer particles (C) are more uniformly dispersed in the thermoplastic resin composition. The impact properties are improved, and the fluidity of the thermoplastic resin composition is further improved. In addition, the interaction between the (meth) acrylic polymer (A), the fatty acid amide (B) and the silicone compound reduces the coefficient of friction of the surface of the obtained resin molded product, and also reduces the thermoplastic resin composition. The elasticity of the product increases, and when the obtained resin molded product comes into contact with an impacted material, the surface of the obtained resin molded product is less likely to be plastically deformed and the contacted portion is less likely to be damaged, so that it is resistant to scratches. Adhesion becomes better.

Furthermore, the thermoplastic resin composition of the present invention can exhibit deep jet-blackness in a molded article obtained by molding the thermoplastic resin composition of the present invention by including carbon black as another additive. .
The type of carbon black is not particularly limited, and known carbon black can be used.
The content ratio of carbon black can be 0.01% by mass or more and 1.5% by mass or less based on the total mass (100% by mass) of the thermoplastic resin composition.

Furthermore, the thermoplastic resin composition of the present invention contains a dye in addition to carbon black as another additive, so that a molded article obtained by molding the thermoplastic resin of the present invention has a greater depth. Jet-blackness can be exhibited.
The dye is not particularly limited, and a known dye can be used. For example, three or more dyes selected from the group consisting of red dyes, yellow dyes, green dyes, blue dyes, and violet dyes can be used in combination.

<Resin molded body>
The resin molded article of the present invention is a resin molded article obtained by molding the thermoplastic resin composition of the present invention.
The method for obtaining the resin molded article of the present invention is not particularly limited. For example, the thermoplastic resin composition of the present invention may be formed by a known molding method such as an injection molding method, an extrusion molding method, and a pressure molding method. There is a method of molding using means. Further, the obtained molded body may be subjected to secondary molding using a known molding method such as a pressure molding method or a vacuum molding method. Molding conditions such as molding temperature and molding pressure may be appropriately set.
Since the resin molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention, the resin molded article has excellent scratch resistance, friction wear and impact resistance.
The resin molded article of the present invention can be used as a vehicle exterior member such as a pillar cover, an instrument cover, a vehicle interior member such as a meter panel, a cosmetic used as an edge band of furniture and the like. Good for products such as materials for housing equipment such as sheets, housings for home appliances, covers for lighting equipment, sanitary goods, front panels or display windows of elastic gaming machines, covers for LED light sources or lamp light sources. Applications where abrasion resistance, abrasion resistance and impact resistance are required.

<Vehicle exterior members>
Since the resin molded article obtained by molding the thermoplastic resin composition of the present invention has excellent scratch resistance, friction wear, and impact resistance, it can be suitably used for a vehicle exterior member for an automobile.
As a vehicle exterior member, for example, a lamp cover such as a head lamp cover and a rear lamp cover; a mirror cover such as a door mirror cover and a fender mirror cover; a visor; a front protector; a front grill; a pillar cover; a license garnish, a front lamp garnish, and a pillar garnish. , Garnishes such as license plate garnish, fog garnish, etc .; rear spoilers; rear grills; and emblems, in which the product is required to have excellent scratch resistance, friction wear and impact resistance.

<Interior components for vehicles>
Since the resin molded article obtained by molding the thermoplastic resin composition of the present invention has excellent scratch resistance, friction wear, and impact resistance, it can be suitably used for a vehicle interior member for an automobile.
Examples of the vehicle interior member include applications in which a product is required to have excellent scratch resistance, friction wear, and impact resistance, such as an instrument cover and a meter panel.

<Vehicle>
Since the vehicle exterior member of the present invention is excellent in scratch resistance, abrasion resistance and impact resistance, the vehicle exterior member can be replaced with a pillar cover, a lamp cover, a mirror cover, a visor, a front protector, a front grill, a garnish. The vehicle including at least one selected from the group consisting of a rear spoiler, a rear grill, and an emblem does not crack or damage the vehicle exterior member during traveling of the vehicle, and is further made of plastic such as polypropylene resin or polyethylene resin in an automatic car washer. When the car is washed by rotating the rotating car wash brush at high speed, the exterior parts for the vehicle are not scratched, so that the weather resistance and glossiness inherent to acrylic resin can be maintained, so that the car can be used for a long time. Can maintain good design properties.
As a specific embodiment, a transparent or translucent headlamp cover or rear lamp cover, and a molded body disposed on at least a part of an outer periphery or an outer frame of the headlamp cover or the rear lamp cover. An automotive design material, wherein the molded article is obtained by molding the thermoplastic resin composition of the present invention.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

<Evaluation method>
The evaluation in Examples and Comparative Examples was performed by the following methods.

<Haze value (Haze value)>
The haze (unit:%) of the test piece was measured using a haze meter (model name: HM-150, manufactured by Murakami Color Research Laboratory) in accordance with ISO14782.

<ΔHaze>
The scratch resistance of the thermoplastic resin composition was evaluated according to the following method.
The thermoplastic resin compositions obtained in Examples and Comparative Examples were supplied to a twin-screw extruder (model name “PCM45”, manufactured by Ikegai Co., Ltd.), kneaded at 250 ° C., and pellets of the thermoplastic resin composition. I got The obtained pellets are supplied to an injection molding machine (model name “FAS-T100D”, manufactured by FANUC CORPORATION), the molding temperature is set to 260 ° C., and the test piece A (width 140 mm, length 140 mm, thickness 3 mm) Plate).
The test piece A thus obtained was set on a flat table, and was subjected to JIS L0849 using a Gakushin-type friction tester (a dyeing fastness tester, model name “RT-200”, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). In accordance with the above, a friction element in which five pieces of Kanekura gauze (trade name, manufactured by Care Life Medical Supply Co., Ltd.) are stacked as a friction element, and as shown in FIG. In the MD direction (flow direction at the time of molding) from the gate position, the friction element is passed through the central part 3 of the test piece 1 under a condition of a load of 500 g so as to pass through the central part of the surface of the test piece. The treated part 2 was formed on the surface of the test piece 1 by reciprocating 130 mm 200 times.
For the test piece A before and after the test, a difference (ΔHaze, unit:%) of the haze value (%) of the processing section 2 was measured according to a method described later. Scratch resistance was determined using the following criteria.
(Judgment criteria)
AA: ΔHaze (%) before and after the test is 0.5 or less A: ΔHaze (%) before and after the test exceeds 0.5 and 1.0 or less B: ΔHaze (%) before and after the test exceeds 1.0

<Dynamic friction coefficient and static friction coefficient>
The dynamic friction coefficient and the static friction coefficient were evaluated according to the following methods as an index of the friction and wear resistance of the thermoplastic resin composition.
A test piece made of a steel plate (material: SK-5, size: 40 mm × 40 mm × 1 mmt) whose surface has been previously polished with a # 1000 sandpaper is superimposed on the test piece A so that the polished surface is on the test piece A side. In accordance with JIS K7125, using a surface property measuring device (model name “Tribogear TYPE-14FW”, manufactured by Shinto Kagaku Co., Ltd.) at a surface pressure of 5.0 N, a moving speed of 100 mm / sec, and a moving distance of 70 mm. The coefficient of dynamic friction and the coefficient of static friction were measured from the load at the time of moving. The average value of the load from 4 seconds to 6 seconds after the start of the movement was used as the dynamic friction coefficient, and the maximum load at the start of the movement of the test piece A was used as the static friction coefficient.
(Criteria for determining dynamic friction coefficient)
A: Dynamic friction coefficient is 0.19 or less B: Dynamic friction coefficient exceeds 0.19 (determination criteria of static friction coefficient)
AA: Coefficient of static friction is less than 0.35 A: Coefficient of static friction is 0.35 or more and 0.40 or less B: Coefficient of static friction exceeds 0.40

<Impact resistance test>
As an index of impact resistance of the thermoplastic resin composition, Charpy at a temperature of 23 ° C. of a test piece B (4.0 mm in width, 80 mm in length, 10.0 mm in thickness, no notch) prepared in accordance with ISO179-1 The impact strength (unit: kJ / m ² ) was measured.
(Judgment criteria)
AA: Charpy impact strength of 50 kJ / m ² or more A: Charpy impact strength of 26 kJ / m ² or more and less than 50 kJ / m ² B: Charpy impact strength of less than 26 kJ / m ²

<Glass transition temperature (T1)>
The glass transition temperature (T1) of the (meth) acrylic polymer (A) was evaluated using a differential scanning calorimeter (DSC) (PerkinElmer, “Diamond DSC”) according to the following method.
About 10 mg of the (meth) acrylic polymer (A) was placed in an aluminum sample container and kept at 20 ° C. for 1 minute. Next, the temperature was raised from 20 ° C. to 180 ° C. at a rate of 10 ° C./min, and maintained at 180 ° C. for 4 minutes. Next, it was cooled at a cooling rate of 10 ° C./min from 180 ° C. to 0 ° C., and kept at 0 ° C. for 4 minutes. Thereafter, the temperature was raised from 0 ° C. to 180 ° C. at a rate of 10 ° C./min, and the glass transition temperature (T1) (unit: ° C.) at this time was determined.

<Melting point of fatty acid amide (B) (T2)>
The melting point (T2) of the fatty acid amide (B) was evaluated according to the following method using a differential scanning calorimeter (DSC) (trade name: DSC-220, manufactured by Seiko Instruments Inc.).
About 10 mg of the fatty acid amide (B) is put in an aluminum sample container, heated to 200 ° C. at a rate of 10 ° C./min, held for 5 minutes and melted, and then cooled to 0 ° C. at 10 ° C./min. After the temperature was lowered, the temperature was raised again at a temperature raising rate of 10 ° C./min, kept for 5 minutes, and lowered at a rate of 10 ° C./min. The maximum point of the crystal melting peak observed at this time was determined by T2).

<Composition ratio of monomer units constituting (meth) acrylic polymer (A)>
The composition ratio of the monomer units (MMA unit and MA unit) constituting the (meth) acrylic polymer (A) was determined by the following procedure using a ¹ H-NMR measurement device (“AVANCE400” manufactured by Bruker). Carried out.
To a concentration of about 5 wt%, the (meth) acrylic polymer (A) was dissolved in chloroform -d ₁ solvent, integration count 32 times, it was measured under conditions of a measurement temperature 20 ° C.. The composition ratio of the MMA unit and the MA unit in the (meth) acrylic polymer (A) was calculated from the integral ratio of the chemical shift in ¹ H-NMR.

<Content ratio of fatty acid amide (B) in thermoplastic resin composition>
The content ratio of the fatty acid amide (B) in the thermoplastic resin composition was measured using a gas chromatography measuring device (GC device) (manufactured by Agilent Technologies, product name: GC7890B, used column: HP-5 manufactured by Agilent J & W). OD 0.32 mm / film thickness 0.25 μm, length 30 m, detector: FID) as follows.
After dissolving 0.2 g of the thermoplastic resin composition in 5 ml of acetone, it was dropped into 30 ml of methanol to obtain a precipitate. Next, the precipitate was removed using a filter paper, and the obtained supernatant solution was used as a sample for GC.
1.0 μl of the GC sample was injected into a GC apparatus (inlet temperature: 280 ° C., detector temperature: 280 ° C., split ratio: 1/50, carrier gas: He), and kept at 80 ° C. for 2 minutes. The temperature was raised to 300 ° C. at a temperature rate of 10 ° C./min. Based on the peak area of fatty acid amide (B) (stearic acid amide) in the obtained gas chromatogram and a calibration curve prepared in advance using a standard solution of fatty acid amide (B) (stearic acid amide) of known concentration, The content ratio (% by mass) of the fatty acid amide (B) (stearic acid amide, palmitic acid amide) contained in the thermoplastic resin composition (100% by mass) was calculated.

(raw materials)
The abbreviations of the compounds used in the examples and comparative examples are as follows.
MMA: Methyl methacrylate (trade name: Acryester M, manufactured by Mitsubishi Chemical Corporation)
ST: Styrene (made by Idemitsu Kosan Co., Ltd.)
BA: n-butyl acrylate (manufactured by Mitsubishi Chemical Corporation)
MA: methyl acrylate (manufactured by Mitsubishi Chemical Corporation)
1,3BDDM: 1,3-butanediol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
AMA: Allyl methacrylate (Mitsubishi Chemical Corporation)
SFS: sodium formaldehyde sulfoxylate polymerization initiator (1): 2,2′-azobis-2-methylbutyronitrile (trade name: V-59, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
n-OM: n-octyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.)
(A-1): (meth) acrylic polymer (1) produced in [Production Example 1] (glass transition temperature T1 = 105 ° C.)
(B-1): stearic acid amide (melting point T2 = 101 ° C.) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(B-2): palmitic amide (melting point T2 = 100 ° C.) (manufactured by Mitsubishi Chemical Corporation)
(B-3): erucamide (melting point T2 = 81 ° C.) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(D-1): Multilayer graft copolymer (D-1) produced in [Production Example 2]
(D-2): Multilayer graft copolymer (D-2) produced in [Production Example 3]
Emulsifier (1): sodium mono-n-dodecyloxytetraoxyethylene phosphate Emulsifier (2): a mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid Partially neutralized sodium hydroxide

[Production Example 1] Production of (meth) acrylic resin (A-1):
900 parts by mass of deionized water, 60 parts by mass of sodium 2-sulfoethyl methacrylate, 10 parts by mass of potassium methacrylate and 12 parts by mass of MMA are added to a reaction vessel equipped with a reflux condenser in which the inside is replaced with nitrogen, and the reaction is carried out with stirring. The temperature in the container was raised to 50 ° C. Thereafter, 0.08 parts by mass of the polymerization initiator (1) was added, and the temperature in the reaction vessel was increased to 60 ° C. while stirring, and then 0.24 parts by mass of MMA was added using a dropping pump. Per minute over 75 minutes. Thereafter, the polymerization was carried out for further 6 hours to obtain a dispersant (solid content: 10% by mass).

  After 2,000 parts by mass of deionized water and 4.2 parts by mass of sodium sulfate were added to a reaction vessel equipped with a reflux condenser equipped with a nitrogen gas inlet tube, the mixture was stirred for 15 minutes at a stirring speed of 320 rpm. Thereafter, 1388.0 parts by mass of MMA (99.0 mol%), 12.0 parts by mass of MA (1.0 mol%), 2.8 parts by mass of the polymerization initiator (1) and a mixture of 4.2 parts by mass of n-OM. The solution was added to the reaction vessel and stirred for 5 minutes. Next, 6.72 parts by mass of the dispersant prepared in Production Example 1 was added to the reaction vessel, followed by stirring to disperse the monomer composition in the reaction vessel in water. Thereafter, the inside of the reaction vessel was replaced with nitrogen.

Next, after the temperature of the liquid in the reaction vessel was raised to 75 ° C., the temperature of the liquid in the reaction vessel was continuously measured and maintained at 75 ° C. until a polymerization exothermic peak was observed. After the polymerization exothermic peak was observed, the temperature in the reaction vessel was raised to 90 ° C., and the temperature was maintained for 60 minutes to carry out polymerization. Thereafter, the mixture in the reaction vessel was filtered, and the filtrate was washed with deionized water and dried at 80 ° C. for 16 hours to obtain a bead-like (meth) acrylic polymer (1).
The (meth) acrylic polymer (1) contained 98% by mass of methyl methacrylate units and 2% by mass of methyl acrylate units. The glass transition temperature (T1) of the (meth) acrylic polymer (1) was 105 ° C., and the weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 100,000.

[Production Example 2] Production of multilayer graft copolymer (D-1):
1. Preparation of Mixture (2-1) 10 parts of ST, 50 parts of BA, 0.2 parts of BDMA, 1.2 parts of AMA, 0.2 parts of CHP, and 2.0 parts of emulsifier (2) were mixed to obtain mixture (2-1). .

2. Preparation of Mixture (2-2) 0.2 parts of SFS and 5 parts of deionized water were mixed to obtain a mixture (2-2).

3. Preparation of Mixture (2-3) 57.0 parts of MMA, 3.0 parts of BA, 0.1 part of DBP, and 0.2 part of n-OM were mixed to obtain a mixture (2-3).

4. Production of Acrylic Copolymer Particles having Multiple Structures In a reaction vessel equipped with a reflux condenser, 300 parts of ion-exchanged water, 0.09 parts of sodium carbonate and 0.9 parts of boric acid were added, and after the temperature was raised to 80 ° C., the mixture ( 2-1) Of 63.6 parts, 3.8 parts were added and held for 15 minutes, and then the remaining mixture (2-1) was continuously added at a rate of 5.1 parts / hour, Thereafter, the temperature was held for one hour to effect polymerization of the innermost layer.

  Next, 5.2 parts of the mixture (2-2) was added, and the mixture was held for 15 minutes. Then, 60.6 parts of the mixture (2-3) was continuously added at a rate of 0.61 part / hour. The polymerization was carried out for the outermost layer while holding for 1 hour to obtain a multi-layer acrylic copolymer latex.

  Next, this latex was coagulated with an aqueous solution of calcium acetate, washed, dehydrated, and dried to obtain a white powdery polymer. This was designated as a multilayer graft copolymer (D-1).

[Production Example 3] Production of multilayer graft copolymer (D-2):
The following components were charged into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer addition port, and a thermometer. (The numbers in parentheses indicate parts by mass. The same applies hereinafter.)
Deionized water (300 parts)
SFS (0.48 parts)
Ferrous sulfate (0.4 × 10 ⁻⁶ parts)
Disodium ethylenediaminetetraacetate (1.2 × 10 ⁻⁶ parts)

Next, the temperature was raised to 80 ° C. while replacing the system with nitrogen, a mixture (e-1) having the following composition was charged over 2 hours, and the mixture was maintained at 80 ° C. for 1 hour to complete polymerization. Latex (L-1) was obtained.
The polymerization rate of the obtained latex (L-1) was 99% or more.
<Mixture (e-1)>
MMA (22 copies)
ST (2.0 copies)
BA (16 copies)
1,3BDDM (1.0 copy)
AMA (0.1 parts)
t-butyl hydroperoxide (0.04 parts)
Sodium mono-n-dodecyloxytetraoxyethylene phosphate (hereinafter also referred to as "emulsifier E") (1.3 parts)

Next, a mixture (e-2) having the following composition was added to the obtained latex (L-1), and the mixture was maintained at 80 ° C. for 15 minutes. The mixture was added dropwise and kept at 80 ° C. for 3 hours to complete the polymerization to obtain a latex (L-2).
The polymerization rate of the obtained latex (L-2) was 99% or more.
<Mixture (e-2)>
SFS (0.2 copy)
Deionized water (5.0 parts)
<Mixture (e-3)>
ST (10 copies)
BA (50 copies)
1,3BDDM (0.2 copy)
AMA (1.2 copies)
Cumene hydroperoxide (0.2 part)
Emulsifier E (2.5 parts)

Next, a mixture (e-4) having the following composition was added to the obtained latex (L-2), and the mixture was maintained at 80 ° C. for 15 minutes, and then a mixture (e-5) having the following composition was taken over 2 hours. The mixture was added dropwise and kept at 80 ° C. for 1 hour to complete the polymerization, thereby obtaining a latex (L-3).
The polymerization rate of the final latex (L-3) obtained was 99% or more.
<Mixture (e-4)>
SFS (0.2 copy)
Deionized water (5.0 parts)
<Mixture (e-5)>
MMA (57.0 parts)
MA (3.0 parts)
t-butyl hydroperoxide (0.1 part)
OcSH (0.2 parts)

A stainless steel container is charged with 300 parts of a 1.6% calcium acetate aqueous solution as a coagulant, heated to 90 ° C. with mixing and stirring, and 300 parts of the final latex (L-3) obtained is continuously added over 10 minutes. Then, the mixture was kept for 5 minutes. Then, the mixture was cooled to room temperature, centrifugally dehydrated at 1,300 G for 3 minutes while washing with deionized water, and filtered to obtain a wet polymer.
The wet polymer was dried at 75 ° C. for 48 hours to obtain a white powdery polymer. This was designated as a multilayer graft copolymer (D-2).

[Example 1]
76 parts by mass of the (meth) acrylic resin (A-1), 24 parts by mass of the multilayer graft copolymer (D-1), and 1.88 parts by mass of the fatty acid amide (B-1) as the fatty acid amide (B). 0.12 parts by mass of the fatty acid amide (B-2) is supplied to a twin-screw extruder (model name “PCM45”, manufactured by Ikegai Co., Ltd.) and kneaded at 250 ° C. to obtain a pellet-shaped thermoplastic resin composition. Was.
Table 2 shows the evaluation results of the obtained thermoplastic resin compositions.
[Example 2]
A pellet-like thermoplastic resin composition was obtained under the same conditions as in Example 1 except that the amount of the fatty acid amide (B-1) was changed to 5.0 parts by mass. Table 2 shows the evaluation results of the obtained thermoplastic resin compositions.

[Comparative Examples 1 and 2]
The same operation as in Example 1 was carried out except that the multilayer graft copolymer (D-1) was not used, to obtain a pellet-shaped thermoplastic resin composition.
Table 2 shows the evaluation results of the obtained thermoplastic resin compositions.

[Comparative Example 3]
The same operation as in Example 1 was performed except that the fatty acid amide (B) was not used, to obtain a pellet-shaped thermoplastic resin composition.
Table 2 shows the evaluation results of the obtained thermoplastic resin compositions.

[Examples 4 to 6, Comparative Examples 4 to 5]
The operation was performed in the same manner as in Example 1 except that the kind and the amount of the fatty acid amide (B) to be used were as shown in Table 1, to obtain a pellet-shaped thermoplastic resin composition.
Table 2 shows the evaluation results of the obtained thermoplastic resin compositions.

The resin molded article obtained by molding the thermoplastic resin composition obtained in Examples 1 and 2 contains (meth) acrylic polymer (A), fatty acid amide (B) and multilayer structure graft copolymer particles (C). Therefore, it was excellent in scratch resistance, friction wear resistance and impact resistance.
On the other hand, the resin molded articles obtained by molding the thermoplastic resin compositions obtained in Comparative Examples 1 and 2 did not contain the multilayer structure graft copolymer particles (C), and thus had insufficient impact resistance.
Since the resin molded article obtained by molding the thermoplastic resin composition obtained in Comparative Example 3 did not contain the fatty acid amide (B), the friction and wear resistance was insufficient.
The molded article obtained by molding the thermoplastic resin compositions obtained in Examples 3 to 6 contains (meth) acrylic polymer (A), fatty acid amide (B), and multilayer structure graft copolymer particles (C). , And excellent in scratch resistance and impact resistance.
Since the fatty acid amide (B) does not satisfy the formula (1) in claim 1, the resin molded article obtained by molding the thermoplastic resin composition obtained in Comparative Example 4 has poor scratch resistance and friction and wear resistance. Was enough.
The resin molded product obtained by molding the thermoplastic resin composition obtained in Comparative Example 5 did not contain the fatty acid amide (B), and thus had insufficient scratch resistance and friction and wear resistance.
In Examples 1-2, 4, 6 and Comparative Examples 1 and 2, the content ratio of the fatty acid amides (B-1) and (B-2) at the time of preparation and the content in the obtained thermoplastic resin composition were as follows. The reason why the content ratio is different is that when the mixture was kneaded with a twin-screw extruder to obtain a pellet-shaped thermoplastic resin composition, it was thermally decomposed or volatilized and removed.

1 Test piece 2 Processing part 3 Central part

Claims (13)

A thermoplastic resin composition containing a (meth) acrylic polymer (A), a fatty acid amide (B), and a multilayer graft copolymer particle (C),
The fatty acid amide (B) is at least one selected from stearic acid amide and palmitic acid amide,
A multilayer structure graft copolymer particle (C) is obtained by forming a rubber-like copolymer (C1) having a crosslinked structure and an alkyl group having 1 to 8 carbon atoms in the presence of the rubber-like copolymer (C1). An outer layer polymer obtained by polymerizing a monomer mixture containing an alkyl acrylate (C2-1) having an ester side chain and an alkyl methacrylate (C2-2) having an alkyl group having 1 to 8 carbon atoms as an ester side chain ( C2), which are fine particles of a multilayer graft copolymer having the following formula: The difference between the glass transition temperature T1 (° C.) of the (meth) acrylic polymer (A) and the melting point T2 (° C.) of the fatty acid amide (B) is represented by the following general formula (1). 2. The thermoplastic resin composition according to claim 1, which is a fatty acid amide satisfying (1).
| T1-T2 | ≦ 10 (1)   The content of the fatty acid amide (B) contained in the thermoplastic resin composition is 0.9% by mass or more and 4.0% by mass or less based on 100% by mass of the total mass of the thermoplastic resin composition. The thermoplastic resin composition according to claim 1.   The fatty acid amide (B) contains at least one selected from stearic acid amide and palmitic amide in a total content of 80% by mass or more based on 100% by mass of the total mass of the fatty acid amide (B). Item 4. The thermoplastic resin composition according to any one of Items 1 to 3.   The fatty acid amide (B) according to any one of claims 1 to 4, wherein the fatty acid amide (B) contains at least 80% by mass or more of stearic acid amide based on 100% by mass of the total mass of the fatty acid amide (B). Exterior members for vehicles.   The said (meth) acrylic polymer (A) is 80-99.5 mass% of repeating units derived from methyl methacrylate with respect to the total mass of this (meth) acrylic polymer (A), and has 2-8 carbon atoms. The thermoplastic resin composition according to any one of claims 1 to 5, comprising 0.5 to 20.0% by mass of a repeating unit derived from an alkyl (meth) acrylate (M) containing an alkyl group as an ester side chain. .   The thermoplastic resin composition according to claim 6, wherein the alkyl (meth) acrylate (M) is methyl acrylate.   A resin molded article comprising the thermoplastic resin composition according to claim 1.   A vehicle exterior member including the resin molded body according to claim 8.   The vehicle exterior member according to claim 9, wherein the exterior member is used for any one selected from the group consisting of a pillar cover, a lamp cover, a mirror cover, a visor, a front protector, a front grill, a garnish, a rear spoiler, a rear grill, and an emblem.   An interior member for a vehicle, comprising the resin molded body according to claim 8.   The vehicle interior member according to claim 11, which is used for any one selected from the group consisting of an instrument cover and a meter panel.   Claims: Used for any one selected from the group consisting of materials for housing equipment, housing for home appliances, covers for lighting equipment, sanitary articles, front panels or display windows of elastic game machines, LED light sources and lamp light source covers. 9. The resin molded article according to 8.