JP7123574B2 - masterbatch particles - Google Patents

Description

TECHNICAL FIELD The present invention relates to masterbatch particles used for engineering plastics having particularly excellent balance of moldability, mechanical properties, slidability and wear resistance, and molded articles obtained from the masterbatch particles.

Engineering plastics such as polyacetal, polyamide, polycarbonate, modified polyphenylene oxide, polyimide, and polyester have high melting points and excellent mechanical properties, so they are widely used in various industrial fields such as the automotive and electrical industries. there is However, among engineering plastics, there are many resins that have poor releasability from the molds used during molding. However, there are problems such as that the molded article is likely to be damaged when it is taken out, and that the appearance of the molded article is poor.

Further, among engineering plastics, there are resins that have low fluidity and cannot be smoothly fed into a molding machine from a hopper of a molding machine used in injection molding or extrusion molding. Therefore, such a resin composition tends to have unstable weighing accuracy, and thus has a problem that the quality of various molded products obtained by molding methods such as injection molding tends to be unstable. .

Conventionally, in order to solve the above problems, a method of adding various release agents and lubricants to the resin has been adopted. Inorganic substances such as metallic stearates and talc, soybean lecithin, natural waxes and synthetic waxes have been used as release agents or lubricants.

In addition, the properties required in the above fields are gradually becoming more sophisticated, and as one example, there is a demand for further improvement in general physical properties as well as in sliding properties. Sliding properties refer to friction and wear properties between resin and metal and between resin and resin.

Sliding properties can be improved by blending fluororesins, polyolefin resins, or lubricating oil additives such as fatty acids, fatty acid esters, silicone oils, and various mineral oils into engineering plastics. In particular, resin compositions containing liquid additives are known to have both excellent slidability with a low coefficient of friction and wear resistance.

For example, in Patent Document 1, for the purpose of providing a resin composition that imparts an engineering plastic molded product with excellent molding processability and a small molding shrinkage, a specific resin and a specific liquid ethylene / α-olefin random combination A resin composition comprising a polymer is disclosed. In addition, Patent Document 2 discloses that it has a low coefficient of friction, excellent slidability, excellent wear resistance, good fluidity and mold releasability, and good molding processability such as no resin stains on the mold. For the purpose of providing an excellent resin composition for molding, a resin composition composed of a specific resin and an oxidatively modified product of a specific liquid ethylene/α-olefin random copolymer has been disclosed.

However, in order to obtain a composition composed of a solid resin and a liquid, melt-kneading using an extruder is common. It was difficult to uniformly mix the liquid additive into the resin.

In such a case, a resin composition in which the liquid additive is uniformly dispersed can generally be obtained by obtaining a masterbatch containing a high concentration of the liquid additive in advance and then adding and blending this masterbatch to the resin.

However, with conventional masterbatches, when a high concentration of liquid additives is added, poor cutting of molten strands, stickiness due to bleeding out to the surface of the masterbatch, and uneven mixing of additives are observed, making handling difficult. rice field. On the other hand, if the liquid additive concentration is lowered to a level that does not cause these problems, the amount of the masterbatch added to the final resin composition will relatively increase, and the final resin will deteriorate due to thermal deterioration of the resin that is the base material of the masterbatch. There is a problem that the mechanical strength of the composition is lowered.

In addition, depending on the resin used as the base material of the masterbatch, the liquid additive may be incorporated into the masterbatch base material in the final resin composition, making it impossible to obtain excellent slidability and wear resistance.
Furthermore, when using engineering plastics containing liquid additives in a high-temperature environment, the liquid additives bleed out onto the surface of the molded product, resulting in a problem of poor appearance.

Japanese Patent No. 2909228 JP-A-11-5912

The present invention solves the above-mentioned problems of the conventional liquid additive masterbatch.
That is, an object of the present invention is to provide a masterbatch of a liquid additive, which enables a high concentration of the liquid additive, is less sticky and is excellent in handleability. Another object of the present invention is to provide a resin composition and a molded article having excellent slidability and wear resistance without impairing the conventional appearance, mechanical properties and moldability of engineering plastics.

As a result of intensive studies, the present inventors found that the above problems can be solved by using a resin composition containing a specific resin and a specific ethylene/α-olefin copolymer in a specific ratio. was completed. Specifically, the present invention includes the following aspects.
[1] (a) A block copolymer containing a polymer block mainly composed of structural units derived from a vinyl aromatic compound and a polymer block mainly composed of structural units derived from a conjugated diene compound, or a hydrogenated product thereof and 70 to 150 parts by mass of an ethylene/α-olefin copolymer (b) having the following characteristics (b1) to (b3) with respect to 100 parts by mass of component (a). is in the range of 100 μm to 1,000 μm.
(b1) Kinematic viscosity at 100° C. is 10 to 5,000 mm ² /s (b2) Content of structural units derived from ethylene is in the range of 30 to 85 mol % (b3) Gel permeation chromatography The molecular weight distribution (Mw/Mn) measured by (GPC) and obtained by polystyrene conversion is 2.5 or less [2] The component (a) is a hydrogenated product of the block copolymer. The masterbatch particles according to [1].
[3] The masterbatch particles according to [1] or [2], wherein the (b) ethylene/α-olefin copolymer has a kinematic viscosity at 100° C. of 500 to 3,000 mm ² /s.
[4] The masterbatch particles according to any one of [1] to [3], wherein the α-olefin in the (b) ethylene/α-olefin copolymer is propylene.
[5] The masterbatch particles according to any one of [1] to [4], wherein the conjugated diene compound is butadiene.
[6] Polyacetal resin, ABS resin, polyamide resin, thermoplastic polyester resin, polyimide resin, polycarbonate resin, and any one of [1] to [5] with respect to 100 parts by mass of the resin 0.5 to 10 parts by mass of masterbatch particles.

According to the present invention, it is possible to provide a masterbatch of a liquid additive that allows a high concentration of the liquid additive, is less sticky and is excellent in handleability. Furthermore, it is possible to provide a resin composition and a molded article having excellent slidability and wear resistance without impairing the conventional mechanical properties and moldability of engineering plastics.

The present invention will be described in detail below.
<Masterbatch particles>
The masterbatch particles of the present invention are (a) a block copolymer containing a polymer block mainly composed of structural units derived from a vinyl aromatic compound and a polymer block mainly composed of structural units derived from a conjugated diene compound. or a hydrogenated product thereof and (b) an ethylene/α-olefin copolymer.

The content of the (b) ethylene/α-olefin copolymer in the masterbatch particles is 70 to 150 parts by weight per 100 parts by weight of the component (a). (b) If the content of the ethylene/α-olefin copolymer is less than 70 parts by mass per 100 parts by mass of the component (a), the amount of the masterbatch blended into the engineering plastic molding will increase, and the mechanical properties of the molding will increase. Physical properties deteriorate. If the content of the (b) ethylene/α-olefin copolymer per 100 parts by mass of the component (a) exceeds 150 parts by mass, the (b) ethylene/α-olefin copolymer will bleed onto the surface of the masterbatch particles. Stickiness and non-uniform mixing due to out occur. The content of the ethylene/α-olefin copolymer (b) is preferably 80 to 140 parts by mass, more preferably 90 to 130 parts by mass, per 100 parts by mass of component (a).

The average particle size of the masterbatch particles according to the present invention is 100 μm to 1,000 μm. If the average particle size exceeds 1,000 μm, the ethylene/α-olefin copolymer (b) bleeds out, making handling difficult. Moreover, when the masterbatch particles are added to the engineering plastic, it may become difficult to uniformly disperse the masterbatch particles in the engineering plastic. If the particle size is less than 100 μm, the adhesion amount to an extruder, an addition line, etc. increases when the masterbatch particles are melt-mixed with an engineering plastic, making it difficult to adjust the addition amount. A preferable range of the average particle diameter of the masterbatch particles according to the present invention is 200 μm to 800 μm, more preferably 200 μm to 700 μm. The average particle size is a numerical value determined by a laser diffraction scattering method.

The average particle size of the masterbatch particles according to the present invention can be adjusted by adjusting the average particle size of the component (a) and the amount of the ethylene/α-olefin copolymer (b) added. The average particle size of component (a) can be adjusted by passing the obtained polymer particles through a metal mesh after polymerization.

<(a) Block Copolymer Containing Polymer Block Mainly Structural Unit Derived from Vinyl Aromatic Compound and Polymer Block Mainly Structural Unit Derived from Conjugated Diene Compound or its Hydrogenated Product>
In the block copolymer or hydrogenated product thereof, which is the component (a) of the masterbatch particles according to the present invention, the block copolymer is a polymer block (hereinafter referred to as Also referred to as "polymer block (A)") and a polymer block (hereinafter also referred to as "polymer block (B)") mainly composed of structural units derived from a conjugated diene compound, Hereinafter, it is also referred to as "(A)/(B) block copolymer".

Specific examples of vinyl aromatic compounds constituting the polymer block (A) include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene and 4-cyclohexylstyrene. , 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, monochlorostyrene, dichlorostyrene, methoxystyrene, indene, acenaphthylene, etc., and one of these vinyl aromatic compounds. One type or two or more types can be used. Of these, styrene is most preferred.

As the conjugated diene compound constituting the polymer block (B), a conjugated diene having 4 to 20 carbon atoms is preferable, and specific examples include butadiene, isoprene, hexadiene, and the like. One type or two or more types can be used. Of these, butadiene and isoprene are more preferable, and butadiene is particularly preferable in order to contain the ethylene/α-olefin copolymer (b) described later at a high concentration.

In addition, the (A)/(B) block copolymer containing the polymer block (A) and the polymer block (B) has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of 30,000 to 500. ,000, more preferably 50,000 to 300,000. When the weight average molecular weight of the (A)/(B) block copolymer is 30,000 or more, the mechanical properties of molded articles obtained from the polymer composition are improved, while when it is 500,000 or less, moldability is obtained. and good workability.

The ratio of the polymer block (A) and the polymer block (B) in the (A)/(B) block copolymer is the number average molecular weight of the (A)/(B) block copolymer, the polymer block (A ) and the number average molecular weight of the polymer block (B), but generally based on the mass of the (A)/(B) block copolymer, the polymer block (A) is 5 to 80% by mass, Polymer block (B) is preferably 20 to 95% by mass, more preferably polymer block (A) is 10 to 75% by mass, and polymer block (B) is 25 to 90% by mass. More preferably, the polymer block (A) is 20 to 40% by mass and the polymer block (B) is 60 to 80% by mass. When the proportion of the polymer block (A) in the (A)/(B) block copolymer is 5% by mass or more (that is, when the proportion of the polymer block (B) is 95% by mass or less), The mechanical properties of the polymer composition containing the (A)/(B) block copolymer and the molded article obtained therefrom are good, and the ratio of the polymer block (A) is 80% by mass or less. When there is (that is, when the proportion of the polymer block (B) is 20% by mass or more), the melt viscosity does not become too high, and moldability and processability are good.

The (A)/(B) block copolymer may be either linear or branched with two or more branches, and has at least one polymer block (A) in the molecule. The structure is not particularly limited as long as it has at least one polymer block (B). An ABA type triblock structure is particularly preferred in view of the balance of mechanical properties, heat resistance and workability.
Specific examples include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-butadiene/isoprene-styrene block copolymers, and the like. For example, a styrene-butadiene-styrene block copolymer means a block copolymer in the form of polystyrene block-polybutadiene block-polystyrene block.

The method for producing the (A)/(B) block copolymer is not particularly limited. can be produced by sequentially polymerizing Examples of the polymerization initiator system in that case include a mixed system of a Lewis acid and an organic compound that generates a cationic polymerization active species by the Lewis acid. Examples of the Lewis acid include titanium tetrachloride, tin tetrachloride, boron trichloride, and aluminum chloride. Examples of the organic compound include organic compounds having a functional group such as an alkoxy group, an acyloxy group, or a halogen group, such as bis(2-methoxy- 2-propyl)benzene, bis(2-acetoxy-2-propyl)benzene, bis(2-chloro-2-propyl)benzene and the like. Furthermore, amides such as N,N-dimethylacetamide and esters such as ethyl acetate may be used as a third component together with the Lewis acids and organic compounds described above, if necessary. As an inert solvent for polymerization, hexane, cyclohexane, methylcyclohexane, methyl chloride, methylene chloride, etc. can be used.

A linear (A)/(B) block copolymer can be prepared, for example, by using (1) a compound having one functional group that generates a Lewis acid and a cationic polymerization active species as a polymerization initiator system, vinyl After polymerizing an aromatic compound to form a polymer block (A), a conjugated diene compound is added to the reaction system and polymerized to form a polymer block (B), and if necessary, further a vinyl aromatic (2) using a Lewis acid as a polymerization initiator system and a compound having two functional groups that generate cationic polymerization active species, First, a conjugated diene compound is polymerized to form a polymer block (B), and then a vinyl aromatic compound is added to the reaction system and polymerized to form a polymer block (A). can be done.

Further, the branched (A) / (B) block copolymer is first conjugated using, for example, a compound having three or more functional groups that generate a Lewis acid and a cationic polymerization active species as a polymerization initiator system. After polymerizing a diene compound to form a polymer block (B), a vinyl aromatic compound is then added and polymerized to form a polymer block (A).

As the component (a) in the polymer composition of the present invention, a hydrogenated product of the (A)/(B) block copolymer can also be used. The use of a hydrogenated product is preferable because the hydrogenation reduces the number of aliphatic double bonds in the (A)/(B) block copolymer, thereby improving the heat resistance and weather resistance.

In the present invention, as the hydrogenated product of the (A)/(B) block copolymer used as the component (a), 90% to 100% of the (A)/(B) block copolymer is an aliphatic di- Those in which the heavy bonds are hydrogenated and 10% or less of the aromatic double bonds are hydrogenated are preferable, particularly those in which 99 to 100% of the aliphatic double bonds are hydrogenated and 5% or less of the aromatic double bonds are hydrogenated. Those in which the heavy bond is hydrogenated are preferred. In such a hydrogenated (A)/(B) block copolymer, the polymer block (B) in which the aliphatic double bond is hydrogenated substantially becomes a block of polyolefin structure.

A known method can be employed for the hydrogenation of the (A)/(B) block copolymer. Examples of the hydrogenation catalyst include nickel, porous diatomaceous earth, Raney nickel, copper dichromate, molybdenum sulfide, and platinum, palladium, etc. supported on a carrier such as carbon.

Hydrogenation can be carried out at any pressure (e.g. atmospheric pressure to 300 atm, preferably 5 to 200 atm), any temperature (e.g. 20°C to 350°C), and any time (e.g. 0.2 to 10 hours). can be done.

As the (A)/(B) block copolymer, two or more (A)/(B) block copolymers having different properties such as molecular weight and styrene content may be used in combination.
Such (A)/(B) block copolymers are commercially available, and these commercial products can be used. Non-hydrogenated products include, for example, Kraton "D series", JSR "TR series", and Asahi Kasei "Tafprene" and "Asaprene". Examples of hydrogenated products include "Septon" and "Hibler" manufactured by Kuraray Co., Ltd., "Tuftec" manufactured by Asahi Kasei Corporation, "Dynalon" manufactured by JSR Corporation, and "G Series" manufactured by Kraton Polymer.

<(b) Ethylene/α-olefin copolymer>
The ethylene/α-olefin copolymer, which is the component (b) of the polymer composition according to the present invention, has a kinematic viscosity at 100°C of 10 to 5,000 mm ² /s, preferably 30 to 3,500 mm ² . /s, more preferably 500 to 3,000 mm ² /s, still more preferably 900 to 2,500 mm ² /s. (b) If the kinematic viscosity at 100° C. of the ethylene/α-olefin copolymer is 10 mm ² /s or more and 5000 mm ² /s or less, the handling of the resulting masterbatch particles and the production of the finally obtained engineering plastic. Very good slidability and wear resistance.

(b) If the kinematic viscosity at 100° C. of the ethylene/α-olefin copolymer exceeds 5,000 mm ² /s, (a) (A)/(B) block copolymer or its hydrogenated product and (b) Compatibility with the ethylene/α-olefin copolymer is reduced, and (b) the dispersibility of the ethylene/α-olefin copolymer is reduced, so that the slidability and abrasion resistance of the resulting engineering plastic are reduced. do.

Further, if the kinematic viscosity at 100° C. of the (b) ethylene/α-olefin copolymer is lower than 10 mm ² /s, the resulting engineering plastic will have poor mechanical properties.
In addition, the (b) ethylene/α-olefin copolymer is structurally similar to the polymer block (B) in which the aliphatic double bonds of the (A)/(B) block copolymer are hydrogenated. , Since it is characterized by being easily entangled with the component (a), it is possible to add the component (b) at a high concentration to the masterbatch composition, and the amount of the masterbatch particles in the engineering plastic can be reduced. It is possible to suppress the influence on the conventional mechanical properties and moldability of engineering plastics.

In the ethylene/α-olefin copolymer (b) according to the present invention, the content of structural units derived from ethylene (hereinafter also referred to as ethylene content) is 30 to 85 mol%, preferably 40 to 75 mol%. , more preferably 40 to 60 mol %. If the ethylene content is too high or too low, the crystallinity will increase and the resulting engineering plastic will have reduced slidability and wear resistance.

(b) The ethylene content of the ethylene/α-olefin copolymer can be measured by the ¹³ C-NMR method. can be identified and quantified. It can also be determined by the FT/IR method described later using an ethylene/α-olefin copolymer whose ethylene content has been quantified in advance based on this method.

The α-olefins constituting the (b) ethylene/α-olefin copolymer include propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1, undecene- 1, α-olefins having 3 to 20 carbon atoms such as dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosene-1, etc. can be exemplified. Two or more of these α-olefins may be used in combination in the ethylene/α-olefin copolymer (b). Among these α-olefins, α-olefins having 3 to 10 carbon atoms are preferred, and propylene is particularly preferred, from the viewpoint of increasing the addition concentration as a masterbatch.

Moreover, the polymerization can be carried out in the presence of at least one other monomer selected from polar group-containing monomers, aromatic vinyl compounds, and cyclic olefins in the reaction system. Other monomers can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on a total of 100 parts by mass of ethylene and an α-olefin having 3 to 20 carbon atoms.

Polar group-containing monomers include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid and maleic anhydride, metal salts such as sodium salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid. α,β-unsaturated carboxylic acid esters such as n-propyl, methyl methacrylate and ethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated glycidyls such as glycidyl acrylate and glycidyl methacrylate; can be exemplified.

Examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, Examples include p-chlorostyrene, divinylbenzene, α-methylstyrene and allylbenzene.

Examples of cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene and tetracyclododecene.

(b) The molecular weight distribution of the ethylene/α-olefin copolymer is measured by gel permeation chromatography (GPC) according to the method described later, and the weight average molecular weight (Mw) and number average molecular weight (Mw) obtained by standard polystyrene conversion are Mn) ratio (Mw/Mn). (b) The molecular weight distribution (Mw/Mn) of the ethylene/α-olefin copolymer is 2.5 or less, preferably 2.3 or less, and more preferably 2.0 or less. If the molecular weight distribution (Mw/Mn) exceeds 2.5 excessively, the volatilization of the low-molecular-weight components during use in a high-temperature environment will lead to deterioration of the mechanical properties of the molded product and/or poor appearance of the surface of the molded product. The molecular weight distribution (Mw/Mn) of the ethylene/α-olefin copolymer (b) is preferably at least 1.4. When the molecular weight distribution is within this range, the (b) ethylene/α-olefin copolymer is excellently dispersed in the masterbatch.

(b) The method for producing the ethylene/α-olefin copolymer is not particularly limited, but it can be prepared from a vanadium compound and an organoaluminum compound as described in JP-B-2-1163 and JP-B-2-7998. and a method using a vanadium-based catalyst. In addition, as a method for producing a copolymer with high polymerization activity, as described in JP-A-61-221207, JP-B-7-121969, JP-A-2796376, retable 2015-147215, etc. A method using a catalyst system comprising a metallocene compound such as zirconocene and an organoaluminumoxy compound (aluminoxane) may also be used.

The polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. Furthermore, it is also possible to carry out the polymerization continuously in two or more polymerization vessels having different reaction conditions.
The molecular weight of the obtained copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5,000 NL per 1 kg of copolymer produced.

(b) The kinematic viscosity at 100° C. of the ethylene/α-olefin copolymer depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity will be high, and if the molecular weight is low, the viscosity will be low. In addition, the molecular weight distribution (Mw/Mn) of the obtained polymer can be adjusted by removing low molecular weight components from the polymer obtained by a conventionally known method such as vacuum distillation. Furthermore, the obtained polymer may be hydrogenated (hereinafter also referred to as hydrogenation) by a conventionally known method. If the double bonds of the polymer obtained by hydrogenation are reduced, the oxidation stability and heat resistance are improved.

The ethylene/α-olefin copolymer (b) may be used singly, or two or more of different molecular weights or different monomer compositions may be used in combination.
In addition, the (b) ethylene/α-olefin copolymer may be graft-modified with functional groups, or these may be further modified secondarily. For example, the methods described in JP-A-61-126120, JP-A-2593264, etc., and secondary modification include the methods described in JP-A-2008-508402.

The masterbatch particles of the present invention can be produced by mixing the above components (a) and (b).
Additives such as heat stabilizers, weather stabilizers, flame retardants, antistatic agents, nucleating agents, coloring agents, foaming agents, fillers, and reinforcing agents are added to the masterbatch particles of the present invention. It can be blended within the range of

The masterbatch particles of the present invention are also excellent in moldability. Therefore, the masterbatch particles of the present invention can be used in a wide variety of applications, and are particularly well-balanced in properties such as abrasion resistance and impact strength, and are suitable for applications requiring these properties.

<Molded body>
The molded article of the present invention is obtained by blending 0.5 to 10 parts by mass of the masterbatch particles described above with 100 parts by mass of engineering plastic, and by various molding methods.
If the content of the masterbatch particles is less than 0.5 parts by mass with respect to 100 parts by mass of the engineering plastic, the molded article will not have sufficient slidability and wear resistance. On the other hand, if it exceeds 10 parts by mass, the mechanical properties of the molded product deteriorate. The content of the masterbatch particles is preferably 0.8 to 8 parts by mass, more preferably 1 to 7 parts by mass, and still more preferably 2 to 6 parts by mass with respect to 100 parts by mass of the engineering plastic.

Molding methods include extrusion molding, injection molding, vacuum molding, blow molding, compression molding, and transfer molding, depending on whether the engineering plastic is a thermoplastic resin or a thermosetting resin. A molding method widely used for thermoplastic resins and thermosetting resins, such as the RIM molding method and the cast molding method, can be selected. Further, when the above resin is a thermosetting resin, the masterbatch particles of the present invention may contain a curing agent, or may contain no curing agent, and after mixing with engineering plastic, the curing agent is used during molding. may be added and mixed. The molded article of the present invention can be molded into containers, trays, sheets, rods, films, fibers, or coatings of various molded articles by various molding methods.

The obtained molded article is excellent in slidability, abrasion resistance and the like.
Applications of the molded product of the present invention include, for example, gears, rotating shafts, bearings, and the like, and textile applications such as belts and cloths.

Examples of molded articles partially or wholly containing the masterbatch of the present invention include radiator grilles, rear spoilers, wheel covers, wheel caps, cowl vent grilles, air outlet louvers, air scoops, hood bulges, fenders and backs. Automotive exterior parts such as doors; cylinder head covers, engine mounts, air intake manifolds, throttle bodies, air intake pipes, radiator tanks, radiator supports, water pump inlets, water pump outlets, thermostat housings, cooling fans , fan shrouds, oil pans, oil filter housings, oil filler caps, oil level gauges, timing belts, timing belt covers and engine compartment parts for automobiles; fuel caps, fuel filler tubes , automotive fuel tanks, fuel sender modules, fuel cut-off valves, quick connectors, canisters, fuel delivery pipes and fuel filler necks; automotive drives such as shift lever housings and propeller shafts System parts; automobile chassis parts such as stabilizer bars and linkage rods; window regulators, door locks, door handles, outside door mirror stays, accelerator pedals, pedal modules, seal rings, bearings, bearing retainers, gears and actuators Automotive functional parts such as wire harnesses, connectors, relay blocks, sensor housings, encapsulations, ignition coils and distributor caps. Automotive interior parts such as; fuel system parts for general-purpose equipment such as fuel tanks for general-purpose equipment (brush cutters, lawn mowers, chain saws, etc.); , various housings, exterior parts, and the like.

Examples of the belt-like formed body include woven belts for seat belt devices used in vehicles, suspension belts for heavy objects such as building materials, safety belts and harnesses, general-purpose belts used for transportation, and the like.

Furthermore, it can be suitably used as a coating agent for moldings that require the aforementioned slidability and wear resistance.
The above engineering plastics include thermoplastic resins such as polyacetal resins, ABS resins, polyamide resins, polyphenylene oxide resins, polyimide resins, thermoplastic polyester resins, polycarbonate resins, epoxy resins, thermosetting unsaturated polyester resins, phenolic resins. thermosetting resins such as These resins are well-known resins per se, as described in publications such as "Engineering Plastics" (edited by Hiroshi Maki and Rikio Kobayashi, published by Sangyo Tosho Co., Ltd.) and "FPR Design Handbook". Its definition is clear. Preferred embodiments of each resin are described below.

(1) Polyacetal resin Polyacetal resin is typically a resin obtained by ring-opening polymerization of formalin or trioxane, optionally together with ethylene oxide, in the presence of a cationic catalyst. As for the resin used as the skeleton, in the present invention, a copolymer type resin is preferred. Such polyacetal resins are commercially available, for example, Iupital (trade name) (Mitsubishi Engineering Plastics Co., Ltd.) and the like can be preferably used in the present invention.

(2) ABS resin ABS resin is typically an impact resistant resin obtained by graft polymerizing acrylonitrile and styrene to polybutadiene. , the weight ratio of the styrene component and the acrylonitrile component (styrene/acrylonitrile) is preferably 70/30 to 80/20. Such ABS resins are commercially available, for example, trade names Stylac (Asahi Chemical Industry Co., Ltd.), Cycolac (Ube Cycon Co., Ltd.), and the like, which can be preferably used in the present invention.

(3) Polyamide resin Polyamide resin is typically a resin obtained by polycondensation of diamine and dicarboxylic acid, or ring-opening polymerization of caprolactam, etc. In the present invention, aliphatic diamine and aliphatic or Polycondensation reactants of aromatic dicarboxylic acids are preferred. Such polyamide resins are commercially available, for example, Leona (trade name, Asahi Chemical Industry Co., Ltd.), Zytel (DuPont Japan Ltd.), and the like, which can be preferably used in the present invention.

(4) Thermoplastic polyester resin Thermoplastic polyester resin is typically a resin obtained by polycondensation of dicarboxylic acid and diol. In the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2, 6-naphthalene dicarboxylate, polycyclohexane terephthalate and the like are preferably used. Such thermoplastic polyester resins are commercially available, for example, Unitika polyester resin (Unitika Ltd.), Rynite (DuPont Japan Ltd.), etc., can be preferably used in the present invention.

(5) Polyphenylene oxide resin Polyphenylene oxide resin is typically a resin obtained by oxidative coupling of 2,6-dimethylphenol in the presence of a copper catalyst, but this resin is blended with other resins. Modified polyphenylene oxide resins modified by a method such as polyphenylene oxide resin can also be used in the present invention. In the present invention, a blend modified product of a styrenic polymer is preferred. Such polyphenylene oxide resins are commercially available, for example, trade names Zylon (Asahi Chemical Industry Co., Ltd.), Iupiace (Mitsubishi Engineering Plastics Co., Ltd.), etc., can be preferably used in the present invention. .

(6) Polyimide resin A polyimide resin is typically a resin obtained by polycondensing a tetracarboxylic acid and a diamine to form an imide bond in the main skeleton. In the present invention, pyromellitic anhydride and diaminodiphenyl ether are preferred. Such polyimide resins are commercially available, for example, the trade name Vespel (DuPont Japan Limited) can be mentioned, and can be preferably used in the present invention.

(7) Polycarbonate resin Polycarbonate resin is typically a resin obtained by reacting an aromatic diol (eg, bisphenol A) with phosgene, but diethylene glycol diallyl carbonate is preferred in the present invention. Such polycarbonate resins are commercially available, for example, NOVAREX (Mitsubishi Chemical Co., Ltd.), Panline (Teijin Chemicals Co., Ltd.), Lexan (Nippon GE Plastics Co., Ltd.), etc. It can be preferably used in the present invention.
The above resins (1) to (7) are thermoplastic resins. The resins (8) to (10) described below are thermosetting resins, and the resins before thermosetting will be described.

(8) Epoxy resin Epoxy resin is typically a resin obtained by reacting an aromatic diol (eg bisphenol A) and epichlorohydrin in the presence of an alkali. Bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin of ∼5000 are preferable. Such epoxy resins are commercially available, and examples thereof include trade names Epiclon (Dainippon Ink and Chemicals, Inc.) and Sumie Epoxy (Sumitomo Chemical Industries, Ltd.), which can be preferably used in the present invention. .

(9) Thermosetting unsaturated polyester resin A thermosetting unsaturated polyester resin is typically a resin obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol. In the invention, resins obtained by esterifying unsaturated dicarboxylic acids such as maleic acid and fumaric acid and diols such as ethylene glycol and diethylene glycol are preferred. Such thermosetting unsaturated polyester resins are commercially available. can be done.

(10) Phenolic resin In the present invention, the phenolic resin includes both so-called novolak type and resol type, but novolak type cured with hexamethylenetetramine and solid resol mainly composed of dimethylene ether bonds are preferred. Such phenolic resins are commercially available, for example, trade names Sumicon PM (Sumitomo Bakelite Co., Ltd.), Nikka Line (Nippon Synthetic Chemical Industry Co., Ltd.), etc., can be preferably used in the present invention. .

As engineering plastics, thermoplastic resins such as polyacetal resins, ABS resins, polyamide resins, thermoplastic polyester resins, polyimide resins and polycarbonate resins are preferred from the viewpoint of uniform dispersion of the masterbatch resin composition.

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to these examples.
[Evaluation method]
In the following examples, comparative examples, etc., the physical properties of the ethylene/α-olefin copolymers were measured by the following methods.

<Ethylene content (mol%)>
Using a Fourier transform infrared spectrophotometer FT/IR-610 or FT/IR-6100 manufactured by JASCO Corporation, absorption near 721 cm ^-1 based on the horizontal vibration of long-chain methylene groups and 1155 cm ^- based on the skeletal vibration of propylene were measured. The absorbance ratio (D1155 cm ^-1 /D721 cm ^-1 ) to the absorption near ¹ was calculated, and the ethylene content based on mass (mass %) was obtained. Next, using the obtained ethylene content (% by mass), the molar-based ethylene content (mol%) was determined according to the following formula.

<Molecular weight distribution (Mw/Mn)>
Molecular weight distribution was measured as follows using Tosoh Corporation HLC-8320GPC. As the separation column, TSKgel SuperMultiporeHZ-M (4 columns) was used, the column temperature was set to 40 ° C., tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the development rate was set to 0.35 ml / min, and the sample concentration was set to The concentration was 5.5 g/L, the sample injection amount was 20 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, one manufactured by Tosoh Corporation (PStQuick MP-M) was used. A weight average molecular weight (Mw) and a number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight according to a general-purpose calibration procedure, and a molecular weight distribution (Mw/Mn) was calculated from these values.

<Viscosity characteristics>
The kinematic viscosity at 100°C was measured and calculated by the method described in JIS K2283.

<Unsaturated bond amount>
Using o-dichlorobenzene-d4 as a measurement solvent, ¹ H-NMR under the measurement conditions of a measurement temperature of 120° C., a spectrum width of 20 ppm, a pulse repetition time of 7.0 seconds, and a pulse width of 6.15 μsec (45° pulse). A spectrum (400 MHz, JEOL ECX400P) was measured. The solvent peak (ortho-dichlorobenzene 7.1 ppm) was used as the chemical shift reference, with the main peak observed at 0-3 ppm and the vinyl, vinylidene, disubstituted and trisubstituted olefins observed at 4-6 ppm. The amount of unsaturated bonds per 1000 carbon atoms (number/1000C) was calculated from the ratio of the integral values of the peaks.

<Average particle size>
The particles of the obtained resin composition were dispersed in methanol, subjected to dispersion treatment for 5 minutes at an output of 25 W using an ultrasonic homogenizer, and then analyzed by a laser beam diffraction scattering method using Microtrac's MT3300EX II to 0.000. The particle size distribution was measured in the measurement range of 021 to 1,408 μm to obtain the average particle size.

<Meeting>
The association of masterbatch particles is defined as the case where the average particle size of the obtained masterbatch particles is in the range of 100 μm to 1,000 μm, and the number of aggregated particles exceeds 30% of the total amount. It was evaluated as "Yes" and "No" when it was 30% or less.

<Sticky>
The stickiness was evaluated by visual inspection and tactile evaluation of the obtained masterbatch particles. evaluated.

<Appearance after heat aging>
The resulting molded articles were heated in an oven in the atmosphere to 120° C. for polyamide resin molded articles and to 100° C. for thermoplastic polyester resin molded articles, and maintained for 168 hours before evaluating the appearance. The notation of the results is as follows.
○: No change in surface appearance ×: Precipitation of oily substance on the surface of the compact

<Impact strength>
Charpy impact strength was measured using notched multi-purpose test pieces in accordance with ISO-179.

<Friction coefficient and specific wear amount>
The coefficient of friction and the amount of specific wear were measured using a Matsubara type friction and wear tester according to JIS K 7218 "Plastic sliding wear test method A". The test conditions were as follows: mating material: S45C, speed: 50 cm/sec, distance: 3 km, load: 15 kg (coefficient of friction) or 2.5 kg (specific wear amount), ambient temperature for measurement: 23°C and 150°C. When the test piece penetrated due to wear, the specific wear amount was expressed as >10,000×10 ⁻³ mm ³ /kgf·km.

<Limit PV value>
The limit PV value was evaluated by the stepwise method [JIS K7218 (SUS ring/resin sheet)]. Specifically, sliding speed: 0.2 m/s, test load: 0.25 to 25 MPa (0.25 MPa per step), test temperature: 23 ° C. The limit PV value was calculated from the test load and the sliding speed until the coefficient of friction increased and the heat generation temperature increased.
[(a) block copolymer containing a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound or a hydrogenated product thereof]
SEBS-1: Polystyrene-poly(ethylene/butylene)-polystyrene block copolymer, Septon (trademark) 8006 manufactured by Kuraray Co., Ltd. (styrene content: 33% by weight, MFR 230° C.: not melted, average particle size: 420 μm )
SEPS: polystyrene-poly(ethylene/propylene)-polystyrene block copolymer, Septon (trademark) 2005 manufactured by Kuraray Co., Ltd. (styrene content: 20% by weight, MFR 230° C.: not melted, average particle size: 400 μm)
SEBS-2: Polystyrene-poly(ethylene/butylene)-polystyrene block copolymer, Septon (trademark) 8007L manufactured by Kuraray Co., Ltd. (styrene content: 30% by weight, MFR 230°C = 2 g/10 min, average particle size of about 3 mm pellet)
[(b) Production of ethylene/α-olefin copolymer]
(b) Ethylene/α-olefin copolymer was produced by the following method.

<Synthesis of Metallocene Compound>
[Synthesis Example 1]
Synthesis of [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)]zirconium dichloride (i) Synthesis of 6-methyl-6-phenylfulvene Nitrogen atmosphere Then, 7.3 g (101.6 mmol) of lithium cyclopentadiene and 100 mL of dehydrated tetrahydrofuran were added to a 200 mL three-necked flask and stirred. The solution was cooled with an ice bath and 15.0 g (111.8 mmol) of acetophenone was added dropwise. After stirring at room temperature for 20 hours, the resulting solution was quenched with dilute aqueous hydrochloric acid. 100 mL of hexane was added to extract the soluble matter, and the organic layer was washed with water and saturated brine and dried over anhydrous magnesium sulfate. Thereafter, the solvent was distilled off, and the resulting viscous liquid was separated by column chromatography (hexane) to obtain the desired product, 6-methyl-6-phenylfulvene (red viscous liquid).

(ii) Synthesis of methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane 2,7-di-t-butylfluorene2. 01 g (7.20 mmol) and 50 mL of dry t-butyl methyl ether were added. 4.60 mL (7.59 mmol) of n-butyllithium/hexane solution (1.65 M) was gradually added while cooling with an ice bath, and the mixture was stirred at room temperature for 16 hours. After adding 1.66 g (9.85 mmol) of 6-methyl-6-phenylfulvene, the mixture was stirred under reflux with heating for 1 hour. 50 mL of water was slowly added with ice bath cooling and the resulting biphasic solution was transferred to a 200 mL separatory funnel. After adding 50 mL of diethyl ether and shaking several times, the aqueous layer was removed, and the organic layer was washed three times with 50 mL of water and once with 50 mL of saturated brine. After drying with anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. When a solution obtained by adding a small amount of hexane was subjected to ultrasonic waves, a solid precipitated, which was collected and washed with a small amount of hexane. Drying under reduced pressure gave 2.83 g of methyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane as a white solid.

(iii) Synthesis of [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)]zirconium dichloride Methyl (cyclopentadienyl) was added to a 100 mL Schlenk tube under a nitrogen atmosphere. Dienyl)(2,7-di-t-butylfluorenyl)(phenyl)methane 1.50 g (3.36 mmol), dehydrated toluene 50 mL and THF 570 μL (7.03 mmol) were sequentially added. 4.20 mL (6.93 mmol) of n-butyllithium/hexane solution (1.65 M) was gradually added while cooling with an ice bath, and the mixture was stirred at 45° C. for 5 hours. The solvent was distilled off under reduced pressure, and 40 mL of dehydrated diethyl ether was added to give a red solution. While cooling in a methanol/dry ice bath, 728 mg (3.12 mmol) of zirconium tetrachloride was added, and the mixture was stirred for 16 hours while gradually raising the temperature to room temperature to obtain a reddish-orange slurry. The solid obtained by evaporating the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After concentrating by distilling off the solvent under reduced pressure, a small amount of hexane was added, and the mixture was allowed to stand at -20°C to precipitate a reddish orange solid. This solid was washed with a small amount of hexane and then dried under reduced pressure to obtain [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfurenyl) as a reddish-orange solid. 1.20 g of olenyl)]zirconium dichloride are obtained.

<Polymerization Example 1>
710 mL of heptane and 145 g of propylene were charged into a stainless steel autoclave having an internal volume of 2 L which had been sufficiently replaced with nitrogen, the temperature in the system was raised to 150° C., and then 0.40 MPa of hydrogen and 0.27 MPa of ethylene were supplied. The total pressure was 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, 0.0001 mmol of [methylphenylmethylene (η ⁵ -cyclopentadienyl)(η ⁵ -2,7-di-t-butylfluorenyl)]zirconium dichloride and N,N- Polymerization was initiated by injecting 0.001 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate with nitrogen and setting the stirring rotation speed to 400 rpm. After that, only ethylene was continuously supplied to keep the total pressure at 3 MPaG, and polymerization was carried out at 150° C. for 5 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene and hydrogen were purged. The resulting polymer solution was washed with 1000 mL of 0.2 mol/L hydrochloric acid three times and then with 1000 mL of distilled water three times, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure.

Further, 100 mL of a hexane solution of 0.5% by mass Pd/alumina catalyst and a polymer dissolved in 500 mL of hexane were added to a stainless steel autoclave having an internal volume of 1 L, and the autoclave was sealed and then purged with nitrogen. Then, the temperature was raised to 140° C. with stirring, and after the inside of the system was replaced with hydrogen, the pressure was raised to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.

After distilling off the solvent of the obtained polymer solution under reduced pressure, it was dried overnight under reduced pressure at 80° C. to obtain 52.2 g of an ethylene-propylene copolymer (polymer 1). Polymer 1 had a content of ethylene-derived structural units of 53.1 mol %, a molecular weight distribution (Mw/Mn) of 1.8, and a kinematic viscosity at 100° C. of 605 mm ² /s. In addition, the amount of unsaturated bonds in polymer 1 was less than 0.1/1000C.

[Engineering plastic]
PA: Polyamide resin, PA6, Amilan CM1007 manufactured by Toray Industries, Inc.
PET: Thermoplastic polyester resin, polyethylene terephthalate, Unitika polyester resin SA-1206 manufactured by Unitika Ltd. (pellets with an average particle size of about 3 mm)
[mineral oil]
Paraffin-based process oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-380, 100° C. kinematic viscosity: 30 mm ² /s)

[Example 1]
100 parts by mass of SEBS-1 and 100 parts by mass of polymer 1 were mixed, heated to 100° C. and allowed to stand for 24 hours to obtain masterbatch particles (MB).

[Example 2]
Masterbatch particles were obtained according to the method of Example 1, except that SEBS-1 was changed to SEPS.

[Example 3]
A masterbatch particle was obtained according to the method of Example 1, except that the blending amount of polymer 1 was changed to 140 parts by mass.

[Comparative Example 1]
Masterbatch particles were obtained according to the method of Example 1, except that SEBS-1 was changed to SEBS-2.

[Comparative Example 2]
A masterbatch particle was obtained according to the method of Example 1, except that the blending amount of polymer 1 was changed to 170 parts by mass.

[Comparative Example 3]
Masterbatch particles were obtained according to the method of Example 1, except that SEBS-1 was changed to PET.
Table 1 shows the average particle size, evaluation of association, and evaluation of stickiness of the masterbatch particles obtained in Examples 1 to 3 and Comparative Examples 1 to 3.
The numerical values shown for SEBS-1, SEPS, SEBS-2, PET and Polymer 1 in Table 1 indicate parts by weight.

[Reference example 1]
PET was used as the base resin for the masterbatch, melted at a cylinder temperature of 280°C using a 15 mmφ twin screw extruder (L/D = 45), and heated to 100°C using a plunger type metering pump. An attempt was made to prepare a masterbatch by feeding a fixed amount of polymer 1 through the vent port of the extruder. When it exceeded, the discharge amount of the molten strand became unstable, and pellets were not obtained. MB-R1 was obtained by adding 5 parts by mass of polymer 1 to 100 parts by mass of PET.

[Example 4, Example 5]
The masterbatch particles (MB) obtained in Example 1 are blended in advance with PA at the mass ratio shown in Table 2, and melt-mixed using the above-mentioned extruder at a cylinder temperature of 240 ° C. to form PA pellets. Created. The obtained pellets were injection-molded into molded pieces, and the obtained molded pieces were evaluated for appearance (appearance after heat aging), mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance ( Specific wear amount, limit PV value) were evaluated. Table 2 shows the results.

[Example 6, Example 7]
The masterbatch particles (MB) obtained in Example 1 were blended in advance with PET at the mass ratio shown in Table 2, melt-mixed using the above-described extruder at a cylinder temperature of 280 ° C., and PET pellets were obtained. Created. The obtained pellets were injection-molded into molded pieces, and the obtained molded pieces were evaluated for appearance (appearance after heat aging), mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance ( Specific wear amount, limit PV value) were evaluated. Table 2 shows the results.

[Comparative Example 4]
The procedure of Example 4 was repeated except that the masterbatch particles (MB) obtained in Example 1 were not used. strength), slidability (coefficient of friction), and wear resistance (specific wear amount, limit PV value) were evaluated. Table 3 shows the results.

[Comparative Example 5]
The same procedure as in Example 6 was performed except that the masterbatch particle pellet (MB) obtained in Example 1 was not used. Impact strength), slidability (coefficient of friction), and wear resistance (specific wear amount, limit PV value) were evaluated. Table 3 shows the results.

[Comparative Example 6]
In the same manner as in Example 6 except that 3 parts by mass of MB-R1 was used instead of 3 parts by mass of the masterbatch particles (MB) obtained in Example 1, the appearance ( Appearance after heat aging), mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance (specific wear amount, limit PV value) were evaluated. Table 3 shows the results.

[Comparative Example 7]
In Comparative Example 7, PA pellets were prepared by feeding polymer 1 and PA heated to 100° C. using a plunger-type metering pump at a mass ratio shown in Table 3 through the vent port of the extruder. . The resulting pellets were injection molded to create a molded piece, and the resulting molded product was evaluated for appearance (appearance after heat aging), mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance ( Specific wear amount, limit PV value) were evaluated. Table 3 shows the results.

[Comparative Example 8]
The procedure was carried out in the same manner as in Comparative Example 7, except that 2 parts by mass of mineral oil was used instead of 2 parts by mass of polymer 1. Appearance (appearance after heat aging), mechanical properties (impact strength) , slidability (friction coefficient), and wear resistance (specific wear amount, limit PV value) were evaluated. Table 3 shows the results.
The numerical values shown for PA, PET, MB, MB-R1, Polymer 1 and mineral oil in Tables 2 and 3 are parts by mass.

As shown in Table 1, in Examples 1 to 3, good masterbatch particles were obtained which were free from aggregation and stickiness and which were excellent in handling. On the other hand, stickiness is observed in Comparative Example 1, in which the average particle size of the masterbatch particles is large, and aggregation and stickiness are observed in Comparative Example 2, in which the content of the ethylene/α-olefin copolymer (b) is excessive. , it was difficult to handle the masterbatch particles.

As shown in Tables 2 and 3, the engineering plastic moldings of Examples 4 to 7 obtained using the masterbatch particles of the present invention are comparative example 4 that does not contain the masterbatch particles of the present invention. and Comparative Example 5, all engineering plastic molded articles had excellent slidability and wear resistance.

As shown in Table 3, Comparative Example 6, in which the pellets obtained in Reference Example 1 were blended, resulted in inferior slidability. In addition, in Comparative Examples 7 and 8, in which polymer 1 and mineral oil, which are oily compounds, were directly added to the engineering plastic, the oily compound bleed out on the surface of the molded piece in a high-temperature environment, resulting in a significantly inferior appearance. became.

Claims (5)

100 parts by mass of either a polyamide resin or a thermoplastic polyester resin;
(a) a block copolymer containing a polymer block mainly composed of structural units derived from a vinyl aromatic compound and a polymer block mainly composed of structural units derived from a conjugated diene compound or a hydrogenated product thereof; Based on 100 parts by mass of component (a), 70 to 150 parts by mass of an ethylene/α-olefin copolymer (b) having the following characteristics (b1) to (b3) is obtained by a laser diffraction scattering method . 0.5 to 10 parts by mass of masterbatch particles having an average particle size of 100 μm to 1,000 μm obtained by measuring the particle size distribution in the measurement range of 0.021 to 1,408 μm were blended and molded. molding .
(b1) Kinematic viscosity at 100° C. is 10 to 5,000 mm ² /s (b2) Content of structural units derived from ethylene is in the range of 30 to 85 mol % (b3) Gel permeation chromatography The molecular weight distribution (Mw/Mn) is 2.5 or less in the molecular weight obtained by polystyrene conversion measured by (GPC) 2. The molded article according to claim 1, wherein the component (a) is a hydrogenated product of the block copolymer. 3. The molded article according to claim 1, wherein the (b) ethylene/α-olefin copolymer has a kinematic viscosity at 100° C. of 500 to 3,000 mm ² /s. The molded article according to any one of claims 1 to 3, wherein the α-olefin of the (b) ethylene/α-olefin copolymer is propylene. The molded article according to any one of claims 1 to 4, wherein the conjugated diene compound is butadiene.