Title of invention: Resin composition for masterbatch
Technical field
[0001]
　The present invention relates to a masterbatch resin composition used for engineering plastics having a particularly excellent balance of moldability, mechanical properties, slidability, and abrasion resistance, and a molded product obtained from the resin composition.
Background technology
[0002]
　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 automobile industry and the electrical industry. There is. However, there are many engineering plastics that are inferior in mold releasability from the mold used at the time of molding, and particularly when a thin-walled molded product or a molded product having a complicated shape is manufactured using such a resin. In the above, there are problems that the molded product is easily damaged when the molded product is taken out from the mold, and the appearance is deteriorated.
[0003]
　In addition, some engineering plastics have low fluidity and cannot be smoothly supplied into the molding machine from the hopper of the molding machine used for injection molding or extrusion molding. Therefore, such a resin composition has a problem that the measurement accuracy tends to be unstable, and the quality of various molded products obtained by a molding method such as injection molding tends to be unstable. ..
[0004]
　Conventionally, in order to solve the above-mentioned problems, a method of adding various mold release agents and lubricants to the resin has been adopted. Conventionally, as the release agent or lubricant, inorganic substances such as stearic acid metal salt and talc, soybean lecithin, natural waxes, synthetic waxes and the like have been used.
[0005]
　Further, the required characteristics in the above-mentioned fields are gradually becoming more sophisticated, and as an example, further improvement of sliding characteristics as well as general physical properties is desired. The sliding property refers to the friction / wear property between the resin and the metal and between the resin and the resin.
[0006]
　The sliding characteristics can be improved by blending a fluororesin, a polyolefin-based resin, or an additive of a lubricating oil such as a fatty acid, a fatty acid ester, a silicone oil, or various mineral oils with an engineering plastic. In particular, it is known that a resin composition containing a liquid additive has both excellent slidability and wear resistance with a low coefficient of friction.
[0007]
　For example, Patent Document 1 discloses a specific resin and a specific liquid ethylene / α-olefin random copolymer for the purpose of providing a resin composition that imparts an engineering plastic molded product having excellent molding processability and a small molding shrinkage rate. A resin composition composed of a polymer is disclosed. Further, Patent Document 2 has a low coefficient of friction, excellent slidability, excellent wear resistance, good fluidity and mold releasability, and mold processability such as no resin stain on the mold. For the purpose of providing an excellent molding resin composition, a resin composition composed of a specific resin and an oxidation-modified product of a specific liquid ethylene / α-olefin random copolymer is disclosed.
[0008]
　However, in obtaining a composition consisting of a solid resin and a liquid, melt kneading using an extrusion molding machine is common, but since the melt viscosity of the resin and the viscosity of the liquid are significantly different, liquid addition is performed. It was difficult to uniformly mix the agent into the resin.
[0009]
　In such a case, generally, a masterbatch containing a high concentration of the liquid additive in advance is obtained, and then this is added and blended with the resin to obtain a resin composition in which the liquid additive is uniformly dispersed.
[0010]
　However, in the conventional masterbatch, when the liquid additive is added at a high concentration, poor cutting of the molten strand, stickiness due to bleeding out to the surface of the masterbatch, and uneven mixing of the additive are observed, which makes handling difficult. rice field. On the other hand, when the concentration of the liquid additive is lowered to a level at which these problems do not occur, the amount of the masterbatch added to the final resin composition increases relatively, and the final resin is thermally deteriorated due to the 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.
[0011]
　Further, 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, and excellent slidability and abrasion resistance may not be obtained.
　Further, when an engineering plastic containing a liquid additive is used in a high temperature environment, there is a problem that the liquid additive bleeds out to the surface of the molded product and impairs the appearance.
Prior art literature
Patent documents
[0012]
Patent Document 1:
Japanese Patent Application Laid-Open No. 2909228 Patent Document 2: Japanese Patent Application Laid-Open No. 11-5912
Outline of the invention
Problems to be solved by the invention
[0013]
　The present invention solves the above-mentioned problems of the conventional masterbatch of liquid additives.
　That is, an object of the present invention is to provide a masterbatch of a liquid additive capable of increasing the concentration of the liquid additive, having less stickiness and excellent handleability. Furthermore, it is an object of the present invention to provide a resin composition and a molded product having excellent slidability and abrasion resistance without impairing the conventional appearance, mechanical characteristics, and moldability of engineering plastics.
Means to solve problems
[0014]
　As a result of diligent studies, the present inventors have obtained a resin composition containing a specific block copolymer or the like, a specific resin, and a specific ethylene / α-olefin copolymer in a specific ratio. We have found that the above problems can be solved, and have completed the present invention. Specific examples of the present invention include the following aspects.
[1] (a) A block copolymer containing a polymer block mainly composed of a structural unit derived from a vinyl aromatic compound and a polymer block mainly composed of a structural unit derived from a conjugated diene compound, or a hydrogenated product thereof. And (b) 40 to 100 parts by mass of the polyolefin resin and (c) ethylene / α-olefin copolymer having the following characteristics (c1) to (c3) with respect to 100 parts by mass of the component (a). A resin composition for a master batch containing 100 to 150 parts by mass.
(C1) The kinematic viscosity at 100 ° C. is 10 to 5,000 mm 2 / s
(c2) The content of structural units derived from ethylene is in the range of 30 to 85 mol%
(c3) Gel permeation chromatography The molecular weight distribution (Mw / Mn) is 2.5 or less in the molecular weight obtained by polystyrene conversion as measured by (GPC).
[2] The component (a) is a hydrogenated product of the block copolymer. The resin composition for a master batch according to [1].
[3] The resin composition for a masterbatch according to [1] or [2], wherein the kinematic viscosity of the ethylene / α-olefin copolymer (c) at 100 ° C. is 500 to 3,000 mm 2 / s.
[4] The resin composition for a masterbatch according to any one of [1] to [3], wherein the α-olefin of the ethylene / α-olefin copolymer (c) is propylene.
[5] The resin composition for a masterbatch according to any one of [1] to [4], wherein the polyolefin-based resin is polypropylene in the first half (b).
[6] The resin composition for a masterbatch according to any one of [1] to [5], wherein the conjugated diene compound is butadiene.
[7] A pellet comprising the resin composition for masterbatch according to any one of [1] to [6], having an average particle size of more than 1 mm and 6 mm or less.
[8] The above-mentioned one of [1] to [6] with respect to any one of a polyacetal resin, an ABS resin, a polyamide resin, a thermoplastic polyester resin, a polyimide resin and a polycarbonate resin, and 100 parts by mass of the resin. A molded product containing 0.5 to 10 parts by mass of a resin composition for a master batch.
[9] A structural unit derived from (a) a vinyl aromatic compound is added to
　100 parts by mass of any one of a polyacetal resin, an ABS resin, a polyamide resin, a thermoplastic polyester resin, a polyimide resin and a polycarbonate resin.
A block copolymer containing a polymer block as a main component and a polymer block mainly composed of a structural unit derived from a conjugated diene compound, or 0.2 to 3 parts by mass of a hydrogenated product thereof, and
(b) polyolefin resin 0. .08 to 3 parts by mass and
(c) 0.2 to 4.5 parts by mass of an ethylene / α-olefin copolymer having the characteristics of (c1) to (c3) above.
　A resin composition in which the content of the component (b) is 40 to 100 parts by mass and the content of the component (c) is 100 to 150 parts by mass per 100 parts by mass of the component (a).
[10] A molded product containing the resin composition according to [9].
The invention's effect
[0015]
　According to the present invention, it is possible to provide a masterbatch of a liquid additive, which can have a high concentration of the liquid additive, has less stickiness, and is excellent in handleability. Further, it is possible to provide a resin composition and a molded product having excellent slidability and abrasion resistance without impairing the conventional mechanical properties and moldability of engineering plastics.
Mode for carrying out the invention
[0016]
　Hereinafter, the present invention will be described in detail.

　The resin composition for master batch of the present invention is mainly composed of (a) a polymer block mainly composed of a structural unit derived from a vinyl aromatic compound and a structural unit derived from a conjugated diene compound. It contains a block copolymer containing a polymer block or a hydrogenated product thereof, (b) a polyolefin-based resin, and (c) an ethylene / α-olefin copolymer.
[0017]
　The composition of the resin composition for a master batch consists of (a) a block containing a polymer block mainly composed of a structural unit derived from a vinyl aromatic compound and a block containing a polymer block mainly composed of a structural unit derived from a conjugated diene compound. With respect to 100 parts by mass of the polymer or its hydrogenated product, (b) the polyolefin-based resin is 40 to 100 parts by mass, and (c) the ethylene / α-olefin copolymer is 100 to 150 parts by mass.
[0018]
　The content of the (b) polyolefin-based resin in the resin composition for masterbatch is 40 to 100 parts by mass with respect to 100 parts by mass of the component (a). (B) If the content of the polyolefin resin with respect to 100 parts by mass of the component (a) is less than 40 parts by mass, cutting defects of the molten strands occur during masterbatch production, and a good masterbatch cannot be obtained. If it exceeds 100 parts by mass, (c) stickiness or non-uniform mixing due to bleed-out of the ethylene / α-olefin copolymer to the surface of the masterbatch occurs. The content of the polyolefin resin (a) with respect to 100 parts by mass of the component (a) is preferably 40 to 80 parts by mass, and more preferably 40 to 70 parts by mass.
[0019]
　The content of the ethylene / α-olefin copolymer (c) is 100 to 150 parts by mass with respect to 100 parts by mass of the component (a). (C) When the content of the ethylene / α-olefin copolymer with respect to 100 parts by mass of the component (a) is less than 100 parts by mass, the amount of the masterbatch compounded in the engineering plastic molded product increases, and the molded product Mechanical properties deteriorate. (C) When the content of the ethylene / α-olefin copolymer with respect to 100 parts by mass of the component (a) exceeds 150 parts by mass, the (c) ethylene / α-olefin copolymer bleeds out to the surface of the masterbatch. Causes stickiness and heterogeneous mixing. The content of the ethylene / α-olefin copolymer with respect to 100 parts by mass of the component (a) is preferably 100 to 144 parts by mass, and more preferably 100 to 140 parts by mass.
[0020]
<(A) a block copolymer containing a polymer block composed mainly of structural units derived from the polymer block and a conjugated diene compound mainly of structural units derived from a vinyl aromatic compound or a hydrogenated product>
　present In the block copolymer or its hydrogenated product which is the component (a) of the resin composition for master batch according to the present invention, the block copolymer is a polymer block mainly composed of a structural unit derived from a vinyl aromatic compound ( Hereinafter, it also has a "polymer block (A)") and a polymer block (hereinafter, also referred to as "polymer block (B)") mainly composed of a structural unit derived from a conjugated diene compound. Hereinafter, it is also referred to as "(A) / (B) block copolymer".
[0021]
　Specific examples of the vinyl aromatic compound 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, inden, acenaphthylene and the like, and one of these vinyl aromatic compounds Type or two or more types can be used. Of these, styrene is the most preferable.
[0022]
　The conjugated diene compound constituting the polymer block (B) is preferably a conjugated diene having 4 to 20 carbon atoms, and specific examples thereof include butadiene, isoprene, and hexadiene. 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 described later (c) at a high concentration.
[0023]
　Further, the (A) / (B) block copolymer containing the polymer block (A) and the polymer block (B) has a polystyrene-equivalent weight average molecular weight (Mw) of 30,000 to 500 as measured by GPC. It is preferably 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 the molded product obtained from the polymer composition are improved, while when it is 500,000 or less, the moldability is improved. And workability is good.
[0024]
　The ratio of the polymer block (A) to the polymer block (B) in the (A) / (B) block copolymer is the number average molecular weight of the (A) / (B) block polymer and the polymer block (A). ) And the number average molecular weight of the polymer block (B), but generally, the polymer block (A) is 5 to 80% by mass based on the mass of the (A) / (B) block copolymer. The polymer block (B) is preferably 20 to 95% by weight, more preferably the polymer block (A) is 10 to 75% by mass and the polymer block (B) is 25 to 90% by weight. It is more preferable that 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, 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 product obtained from the polymer composition are good, while the proportion of the polymer block (A) is 80% by mass or less. If there is (that is, if the proportion of the polymer block (B) is 20% by mass or more), the melt viscosity does not become too high and the moldability and processability are good.
[0025]
　The (A) / (B) block copolymer may be either linear or branched into two or more, and may be combined with at least one polymer block (A) in the molecule. It suffices to have at least one polymer block (B), and its structure is not particularly limited. The ABA type triblock structure is particularly preferable from the viewpoint of the balance between mechanical properties, heat resistance and workability.
[0026]
　Specific examples thereof include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and styrene-butadiene / isoprene-styrene block copolymers. For example, the styrene-butadiene-styrene block copolymer means a block copolymer in the form of polystyrene block-polybutadiene block-polystyrene block.
[0027]
　The method for producing the (A) / (B) block copolymer is not particularly limited, but for example, a vinyl aromatic compound such as styrene and a conjugated diene compound such as butadiene are used in an inert solvent using an appropriate polymerization initiator system. Can be produced by sequentially polymerizing and. An example of the polymerization initiator system in that case is a mixed system of Lewis acid and an organic compound that produces a cationically polymerizable active species by Lewis acid. The Lewis acid includes titanium tetrachloride, tin tetrachloride, boron trichloride, aluminum chloride and the like, and the organic compound includes an organic compound having a functional group such as an alkoxy group, an acyloxy group or a halogen, for example, bis (2-methoxy-). Examples thereof include 2-propyl) benzene, bis (2-acetoxy-2-propyl) benzene, and bis (2-chloro-2-propyl) benzene. Further, along with the above-mentioned Lewis acid and the organic compound, amides such as N, N-dimethylacetamide and esters such as ethyl acetate may be used as the third component, if necessary. Further, as the inert solvent for polymerization, hexane, cyclohexane, methylcyclohexane, methyl chloride, methylene chloride and the like can be used.
[0028]
　The linear (A) / (B) block copolymer is made of vinyl by using, for example, (1) a compound having one functional group for producing Lewis acid and a cationic polymerization active species as a polymerization initiator system. After polymerizing the aromatic compound to form the polymer block (A), the conjugated diene compound is added to the reaction system and polymerized to form the polymer block (B), and further vinyl aromatic if necessary. A method of adding a compound and carrying out polymerization to form a polymer block (A), (2) using a compound having two functional groups for producing Lewis acid and a cationic polymerization active species as a polymerization initiator system, First, the 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.
[0029]
　Further, the branched (A) / (B) block copolymer is first conjugated by using, for example, a compound having three or more functional groups for producing Lewis acid and a cationic polymerization active species as a polymerization initiator system. It can be produced by a method such as polymerizing a diene compound to form a polymer block (B) and then adding a vinyl aromatic compound to carry out polymerization to form a polymer block (A).
[0030]
　In the polymer composition of the present invention, as the component (a), the hydrogenated additive of the block copolymer (A) / (B) described above can also be used. When a hydrogenated additive is used, it is preferable in that the hydrogenation reduces the aliphatic double bonds in the (A) / (B) block copolymer, thereby improving the heat resistance and the weather resistance.
[0031]
　In the present invention, the hydrogenated agent of the (A) / (B) block copolymer used as the component (a) is a 90% to 100% aliphatic double bond of the (A) / (B) block copolymer. It is preferable that the double bond is hydrogenated and 10% or less of the aromatic double bond is hydrogenated, and in particular, 99 to 100% of the aliphatic double bond is hydrogenated and 5% or less of the aromatic double bond is hydrogenated. Hydrogenated double bonds are preferred. In such hydrogenated block copolymers (A) / (B), the polymer block (B) to which an aliphatic double bond is hydrogenated is substantially a block having a polyolefin structure.
[0032]
　A known method can be adopted for hydrogenation of the (A) / (B) block copolymer. Examples of the hydrogenation catalyst include nickel, porous diatomaceous earth, Raney nickel, copper dichromate, molybdenum sulfide and the like, and those in which platinum, palladium and the like are supported on a carrier such as carbon.
[0033]
　Hydrogenation should be performed at an arbitrary pressure (for example, atmospheric pressure to 300 atm, preferably 5 to 200 atm), an arbitrary temperature (for example, 20 ° C. to 350 ° C.), and an arbitrary time (for example, 0.2 hour to 10 hours). Can be done.
[0034]
　As the (A) / (B) block copolymer, two or more types of (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 commercially available products can be used. Non-hydrogenated products include, for example, Clayton's "D series", JSR's "TR series", and Asahi Kasei's "Tough Plane" and "Asaprene". Hydrogenated products include, for example, Kuraray's "Septon" and "Hybler", Asahi Kasei's "Tough Tech", JSR's "Dynaron", and Kraton Polymer's "G Series".
[0035]
<(B) Polyolefin-based resin>
　The (b) polyolefin-based resin according to the present invention is preferably a polymer mainly composed of an olefin and having an MFR of 0.1 to 500 g / 10 minutes. (B) The polyolefin-based resin is not particularly limited, and various known olefin-based polymers can be used. For example, ethylene, propylene, butene-1, butene-1, 4-methyl-1-pentene, hexene-1, heptene-1, octene-1, decene-1, undecene-1, dodecene-1, tridecene-1, Examples thereof include homopolymers or copolymers of α-olefins having 2 to 20 carbon atoms such as tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, and eicosen-1. .. Specifically, high-pressure low-density polyethylene, linear low-density polyethylene (so-called LLDPE), medium-density polyethylene, high-density polyethylene, polypropylene, polypropylene random copolymer, poly 1-butene, poly 4-methyl / 1-pentene. , Alone or two or more olefin polymers such as low crystalline or amorphous ethylene / propylene random copolymer, ethylene / butene-1 random copolymer, propylene / butene-1 random copolymer. Examples of the composition include an ethylene / vinyl acetate copolymer (EVA), an ethylene / (meth) acrylic acid copolymer or a metal salt thereof, and an ethylene-cyclic olefin copolymer.
　Further, (b) the polyolefin-based resin may contain a non-conjugated diene as a copolymerization component of the olefin. Specific examples of the non-conjugated diene include 1,4-hexadiene, 1,6-octadene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6. -Chain non-conjugated diene such as octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroinden, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene , 6-Chloromethyl-5-isopropenyl-2-norbornene and other cyclic non-conjugated diene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl- Examples thereof include trienes such as 2,2-norbornene, 1,3,7-octatriene and 1,4,9-decatorien. Of these, 1,4-hexadiene and cyclic non-conjugated diene, particularly dicyclopentadiene and 5-ethylidene-2-norbornene, are preferably used.
　Furthermore, these polyolefin resins may be polymers graft-modified with polar compounds such as maleic acid and silane compounds. Among these, a polymer or copolymer of an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms is desirable.
[0036]
　The ultimate viscosity [η] of such a polyolefin resin (b) measured in decalin at 135 ° C. is not particularly limited, but is preferably 0.5 dl / g or more and 5 dl / g or less. If the ultimate viscosity [η] measured in decalin at 135 ° C. becomes too small, the mechanical strength of the polymer composition decreases. If the ultimate viscosity [η] becomes too large, the moldability deteriorates.
[0037]
　Preferable examples of such (b) polyolefin-based resin include polyethylene, polypropylene, polybutene, etc. Among them, polypropylene-based resin, which is a polymer or copolymer mainly composed of propylene, has a polymer composition. It is preferable in terms of improving the heat resistance and mechanical strength of the object and improving the solidification rate.
[0038]
　Examples of the polypropylene-based resin include a propylene homopolymer and a copolymer of propylene and ethylene and at least one monomer selected from α-olefins having 4 to 20 carbon atoms. When the polypropylene-based resin is a copolymer, the constituent unit derived from propylene is preferably 90 mol% or more, more preferably 93 to 99 mol%.
[0039]
　In the present invention, (b) the MFR (melt flow rate) of the polyolefin-based resin is a value measured in accordance with JIS K7210, and is 190 ° C. for polyethylene (a polymer or copolymer mainly composed of ethylene), 2 It means the value measured under the condition of .16 kg load, and the value measured under the condition of 230 ° C. and 2.16 kg load for polyolefin resin other than polyethylene such as polypropylene.
　The polyolefin-based resin (b) according to the present invention may be a combination of two or more kinds of polyolefin-based resins having different types and properties such as MFR.
[0040]
<(C) Ethylene / α-olefin copolymer>
　The ethylene / α-olefin copolymer, which is the component (c) 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, and even more preferably 900 to 2,500 mm 2 / s. (C) When the kinematic viscosity of the ethylene / α-olefin copolymer at 100 ° C. is 10 mm 2 / s or more and 5000 mm 2 / s or less, the obtained resin composition for masterbatch can be handled and finally obtained. The slidability and abrasion resistance of engineering plastics are extremely good.
[0041]
　(C) When the kinematic viscosity of the ethylene / α-olefin copolymer at 100 ° C. exceeds 5,000 mm 2 / s, the (a) (A) / (B) block copolymer or its hydrogenated product and (c) ) The compatibility with the ethylene / α-olefin copolymer is lowered, and (c) the dispersibility of the ethylene / α-olefin copolymer is lowered, so that the slidability and abrasion resistance of the obtained engineering plastic are improved. descend.
[0042]
　Further, if (c) the kinematic viscosity of the ethylene / α-olefin copolymer at 100 ° C. is lower than 10 mm 2 / s, the mechanical properties of the obtained engineering plastic are lowered.
　Further, the structure of the (c) ethylene / α-olefin copolymer is similar to that of the polymer block (B) in which the aliphatic double bond of the (A) / (B) block copolymer is hydrogenated. , (A) has a characteristic of being easily entangled with the component, so that the component (c) can be added in a high concentration to the composition for the masterbatch, and the amount of the masterbatch compounded in the engineering plastic can be reduced. It is possible to suppress the influence of plastics on the conventional mechanical properties and moldability.
[0043]
　Further, the ethylene / α-olefin copolymer (c) according to the present invention has a content of structural units derived from ethylene (hereinafter, also referred to as ethylene content) of 30 to 85 mol%, preferably 40 to 75 mol%. , More preferably 40-60 mol%. If the ethylene content is too high or too low, the crystallinity will be high and the slidability and wear resistance of the resulting engineering plastic will be reduced.
[0044]
　(C) The ethylene content of the ethylene / α-olefin copolymer can be measured by the 13 C-NMR method, and peaks according to the method described in, for example, the "Polymer Analysis Handbook" (P163-170 published by Asakura Shoten). Can be identified and quantified. Further, 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.
[0045]
　Further, as the α-olefin constituting the (c) ethylene / α-olefin copolymer, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, decene-1, undecene- 1. Dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, eicosen-1, and other α-olefins having 3 to 20 carbon atoms. It can be exemplified. (C) Two or more of these α-olefins may be used in combination in the ethylene / α-olefin copolymer. Among these α-olefins, α-olefins having 3 to 10 carbon atoms are preferable, and propylene is particularly preferable, in terms of increasing the concentration of addition as a resin composition for a masterbatch.
[0046]
　Further, in producing (c) an ethylene / α-olefin copolymer by polymerizing ethylene and α-olefin, at least one other selected from a polar group-containing monomer, an aromatic vinyl compound, and a cyclic olefin. It is also possible to allow the monomer of the above to coexist in the reaction system to proceed with the polymerization. The other monomer can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less, with respect to a total of 100 parts by mass of ethylene and the α-olefin having 3 to 20 carbon atoms.
[0047]
　Examples of the polar group-containing monomer 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, etc. Can be exemplified.
[0048]
　Examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, and hydroxystyrene. Examples thereof include p-chlorostyrene, divinylbenzene, α-methylstyrene, and allylbenzene.
[0049]
　Examples of the cyclic olefin 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.
[0050]
　(C) The molecular weight distribution of the ethylene / α-olefin copolymer was measured by gel permeation chromatography (GPC) according to the method described later, and the weight average molecular weight (Mw) and the number average molecular weight (Mw) obtained by standard polystyrene conversion were obtained. It is calculated as a ratio of Mn) (Mw / Mn). (C) 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 mechanical properties of the molded product deteriorate due to the volatilization of low molecular weight components in use in a high temperature environment, and / or the appearance of the molded product surface deteriorates. Further, (c) the molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer is preferably at least 1.4 or more. When the molecular weight distribution is in this range, (b) the dispersion of the ethylene / α-olefin copolymer in the resin composition for masterbatch is excellent.
[0051]
　(C) The method for producing the ethylene / α-olefin copolymer is not particularly limited, but from the vanadium compound and the organoaluminum compound as described in JP-A-21163 and JP-A-2-7998. There is a vanadium-based catalyst method. Further, as a method for producing a copolymer with high polymerization activity, as described in JP-A-61-221207, Japanese Patent Application Laid-Open No. 7-121969, Japanese Patent No. 2796376, Japanese Patent Application Laid-Open No. 2015-147215, etc. A method using a catalytic system composed of a metallocene compound such as zirconosen and an organoaluminum oxy compound (aluminoxane) may be used.
[0052]
　The polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization continuously in two or more polymerizers 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 amount thereof is appropriately about 0.001 to 5,000 NL per 1 kg of the copolymer to be produced.
[0053]
　(C) The kinematic viscosity of the ethylene / α-olefin copolymer at 100 ° C. depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity is high, and if the molecular weight is low, the viscosity is low. Therefore, the kinematic viscosity at 100 ° C. is adjusted by the above-mentioned molecular weight adjustment. Further, the molecular weight distribution (Mw / Mn) of the obtained polymer can be adjusted by removing the low molecular weight component of the polymer obtained by a conventionally known method such as vacuum distillation. Further, the obtained polymer may be hydrogenated (hereinafter, also referred to as hydrogenation) by a conventionally known method. If the double bond of the polymer obtained by hydrogenation is reduced, the oxidative stability and heat resistance are improved.
[0054]
　(C) The ethylene / α-olefin copolymer may be used alone or in combination of two or more having different molecular weights or different monomer compositions.
　Further, in the (c) ethylene / α-olefin copolymer, functional groups may be graft-modified, or these may be further secondary-modified. Examples of these modification methods include the methods described in JP-A-61-126120 and Japanese Patent No. 2593264, and examples of the secondary modification include methods described in JP-A-2008-508402. Can be mentioned.
[0055]
　The resin composition for a masterbatch of the present invention contains additives such as heat-resistant stabilizers, weather-resistant stabilizers, flame retardants, antistatic agents, nucleating agents, coloring agents, foaming agents, fillers, and reinforcing agents. It can be blended within a range that does not impair the purpose.
　The resin composition for a masterbatch of the present invention is excellent in molding processability. Therefore, the resin composition for masterbatch of the present invention can be widely used in various applications, and is particularly excellent in the balance of properties such as abrasion resistance and impact strength, and is suitable for applications in which these are required.
[0056]

　The pellet according to the present invention comprises the above-mentioned resin composition for masterbatch.
　The average particle size of the pellets according to the present invention is more than 1 mm and 6 mm or less. It is more preferably 2 to 5 mm, still more preferably 2.5 to 3.5 mm. When the average particle size of the pellets exceeds 1 mm and is 6 mm or less, the pellets can be sufficiently kneaded with an extruder or an injection molding machine. The shape of the thermoplastic resin pellet of the present invention is not particularly limited, but as an example, the diameter exceeds 1 mm and is 6 mm or less, preferably 1.5 to 4 mm, and the length is 2 to 6 mm, preferably 2.5 to 4 mm. Examples include a cylindrical shape of the above, and a rectangular parallelepiped shape having a length and a width of 3 to 6 mm and a thickness of 1.5 to 3 mm. The average particle size of the pellets can be appropriately adjusted by adjusting the cutting speed at the time of pelletizing after kneading with an extruder.
　The average volume, average length and average particle size of the pellets can be measured and calculated by the following methods.
[0057]
50 arbitrary pellets are taken out, the weight and specific weight are measured, and the average volume of pellets is calculated by dividing the weight by the specific weight (weight / specific weight). The specific gravity of the pellets can be measured according to JIS K 7112.
[0058]
50 arbitrary pellets can be taken out, the length of each pellet can be measured with a caliper, and the average value of the lengths of all pellets can be calculated.
[0059]
50 arbitrary pellets are taken out, and the maximum diameter (major diameter in the case of an ellipse) and the minimum diameter (minor diameter in the case of an ellipse) of each pellet are measured with a caliper. The average value of the particle size of all pellets is calculated by using the average value of the maximum diameter and the minimum diameter as the particle size of the pellets.
[0060]

　The molded article of the present invention can be obtained by blending 0.5 to 10 parts by mass of the above-mentioned resin composition for masterbatch with 100 parts by mass of engineering plastic and various molding methods.
　If the content of the resin composition for masterbatch is less than 0.5 parts by mass with respect to 100 parts by mass of engineering plastic, sufficient slidability and abrasion resistance cannot be obtained for the molded product. Further, if it exceeds 10 parts by mass, the mechanical properties of the molded product deteriorate. The content of the resin composition for the masterbatch is preferably 0.8 to 8 parts by mass, more preferably 1 to 7 parts by mass, and further preferably 2 to 6 parts by mass with respect to 100 parts by mass of the engineering plastic.
[0061]
　The molding method includes an extrusion molding method, an injection molding method, a vacuum molding method, a blow molding method, a compression molding method, and a transfer molding method, depending on whether the engineering plastic is a thermoplastic resin or a thermosetting resin. A molding method widely and generally used for thermoplastic resins and thermosetting resins, such as a RIM molding method and a casting molding method, can be selected. When the resin is a thermosetting resin, the resin composition for master batch of the present invention may contain a curing agent, or may be mixed with an engineering plastic without containing a curing agent, and then at the time of molding. A curing agent may be added and mixed. The molded product of the present invention can be made into a container shape, a tray shape, a sheet shape, a rod shape, a film shape, a fibrous shape, a coating of various molded products, or the like by various molding methods.
[0062]
　The molded product of the present invention is excellent in slidability, abrasion resistance and the like.
　Examples of applications of the molded product of the present invention include applications such as gears, rotating shafts and bearings, and textile applications such as belts and cloths, but it can also be used in applications where the above characteristics are not required.
[0063]
　Examples of molded products containing the resin composition for master batch of the present invention in part or in whole include a radiator grill, a rear spoiler, a wheel cover, a wheel cap, a cowl vent grill, an air outlet louver, an air scoop, and a hood bulge. , Fenders, back doors and other automotive exterior parts; cylinder head cover, engine mount, air intake manifold, throttle body, air intake pipe, radiator tank, radiator support, water pump inlet, water pump outlet, thermostat Automotive engine room parts such as housings, cooling fans, fan shrouds, oil pans, oil filter housings, oil filler caps, oil level gauges, timing belts, timing belt covers and engine covers; fuel caps, Automotive fuel system parts such as fuel filler tubes, automobile fuel tanks, fuel sender modules, fuel cutoff valves, quick connectors, canisters, fuel delivery pipes and fuel filler necks; shift lever housings and propeller shafts, etc. Automotive drive system parts; Automotive 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 , Automotive functional parts such as gears and actuators; Automotive electronics parts such as wire harness connectors, relay blocks, sensor housings, encapsulations, ignition coils and distributor caps; Instrument panel covers, air conditioner outlets, various operations Interior parts for automobiles such as panels and housings; fuel system parts for general-purpose equipment such as fuel tanks for general-purpose equipment (cutting machines, radiators, chainsaws, etc.); and connectors, LED reflectors, etc.Examples include electrical and electronic parts, electrical and electronic parts, building material parts, various housings, and exterior parts.
[0064]
　Examples of the strip-shaped molded body include a woven belt for a seatbelt device used for a vehicle, a hanging belt for a heavy object such as a building material, a safety belt and a harness, and a general-purpose belt used for transportation.
[0065]
　Further, it can be suitably used as a coating agent for molded products that require the above-mentioned slidability and wear resistance.
　Examples of the above-mentioned engineering plastics include thermoplastic resins such as polyacetal resin, ABS resin, polyamide resin, polyphenylene oxide resin, polyimide resin, thermoplastic polyester resin and polycarbonate resin, and epoxy resin, thermosetting unsaturated polyester resin and phenol resin. And the like, the heat-curable resin can be mentioned. These resins are well-known resins themselves, as described in publications such as "Engineering Plastics" (edited by Makihiro and Rikio Kobayashi, published by Sangyo Tosho Co., Ltd.) and "FPR Design Handbook". The definition is clear. Hereinafter, preferred embodiments of each resin will be described.
[0066]
(1) Polyacetal resin The
　polyacetal resin is typically a resin obtained by ring-opening polymerization of formalin or trioxane together with ethylene oxide in the presence of a cation catalyst, and mainly contains a polyoxymethylene chain. Although it is a resin having a skeleton, in the present invention, a copolymer type resin is preferable. Such polyacetal resins are commercially available, and examples thereof include trade name Iupital (Mitsubishi Engineering Plastics Co., Ltd.), which can be preferably used in the present invention.
[0067]
(2) ABS resin The
　ABS resin is typically an impact-resistant resin obtained by graft-polymerizing acrylonitrile and styrene on polybutadiene, but in the present invention, the polybutadiene component is 5 to 40% by weight. , The weight ratio of the styrene component to the acrylonitrile component (styrene / acrylonitrile) is preferably 70/30 to 80/20. Such ABS resins are commercially available, and examples thereof include trade names such as Stylac (Asahi Kasei Kogyo Co., Ltd.) and Psycholac (Ube Psycon Co., Ltd.), which can be preferably used in the present invention.
[0068]
(3) Polyamide resin The
　polyamide resin is typically a resin obtained by polycondensation of diamine and dicarboxylic acid, ring-open polymerization of caprolactam, etc., but in the present invention, aliphatic diamine and aliphatic or aliphatic or A polycondensation reaction product of an aromatic dicarboxylic acid is preferable. Such polyamide resins are commercially available, and examples thereof include trade names Leona (Asahi Kasei Kogyo Co., Ltd.) and Zytel (Dyupon Japan Limited), which can be preferably used in the present invention.
[0069]
(4) Thermoplastic Polyester Resin The
　thermoplastic polyester resin is typically a resin obtained by polycondensing dicarboxylic acid and diol, but in the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2, 6-Naphthalenedicarboxylate, polycyclohexane terephthalate and the like are preferably used. Such thermoplastic polyester resins are commercially available, and examples thereof include trade names Unitika polyester resin (Unitika Ltd.) and linite (Dyupon Japan Limited), which can be preferably used in the present invention.
[0070]
(5) Polyphenylene Oxide Resin The
　polyphenylene oxide resin is typically a resin obtained by oxidatively coupling 2,6-dimethylphenol in the presence of a copper catalyst, but this resin is blended with another resin. A modified polyphenylene oxide resin modified by a method such as the above can also be used in the present invention. In the present invention, a blended product of a styrene-based polymer is preferable. Such polyphenylene oxide resins are commercially available, and examples thereof include trade names Zylon (Asahi Kasei Kogyo Co., Ltd.) and Upiece (Mitsubishi Engineering Plastics Co., Ltd.), which can be preferably used in the present invention. ..
[0071]
(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. However, in the present invention, pyromellitic anhydride is used. And diaminodiphenyl ether are preferable. Such a polyimide resin is commercially available, and examples thereof include the trade name Vespel (Dyupon Japan Limited), which can be preferably used in the present invention.
[0072]
(7) Polycarbonate Resin The
　polycarbonate resin is typically a resin obtained by reacting an aromatic diol (for example, bisphenol A) with phosgene, but in the present invention, diethylene glycol diallyl carbonate is preferable. Such polycarbonate resins are commercially available, and examples thereof include trade names NOVAREX (Mitsubishi Chemical Corporation), Panline (Teijin Chemicals Ltd.), Lexan (Nippon GE Plastics Ltd.), and the like. 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 those in a state before thermosetting will be described.
[0073]
(8) Epoxy resin The
　epoxy resin is typically a resin obtained by reacting an aromatic diol (for example, bisphenol A) with epichlorohydrin in the presence of an alkali. In the present invention, the epoxy equivalent is 170. ~ 5000 bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are preferable. Such epoxy resins are commercially available, and examples thereof include trade names Epicron (Dainippon Ink and Chemicals Co., Ltd.) and Sumiepoxy (Sumitomo Chemical Co., Ltd.), which can be preferably used in the present invention. ..
[0074]
(9) Thermosetting Unsaturated Polyester Resin The
　thermosetting unsaturated polyester resin is typically a resin obtained by subjecting an aliphatic unsaturated dicarboxylic acid to an aliphatic diol in an esterification reaction. In the present invention, a resin obtained by esterifying an unsaturated dicarboxylic acid such as maleic acid or fumaric acid with a diol such as ethylene glycol or diethylene glycol is preferable. Such thermosetting unsaturated polyester resins are commercially available, and examples thereof include trade names Rigolac (Showa High Polymer Co., Ltd.) and Sumicon (Sumitomo Bakelite Co., Ltd.), which are preferably used in the present invention. Can be done.
[0075]
(10) Phenol resin The
　phenol resin includes both a so-called novolac type and a resol type in the present invention, but a novolac type cured with hexamethylenetetramine and a solid resol mainly composed of a dimethylene ether bond are preferable. Such phenolic resins are commercially available, and examples thereof include trade names Sumicon PM (Sumitomo Bakelite Co., Ltd.) and Nikkaline (Nippon Synthetic Chemical Industry Co., Ltd.), which can be preferably used in the present invention. ..
[0076]
　As the engineering plastic, thermoplastic resins such as polyacetal resin, ABS resin, polyamide resin, thermoplastic polyester resin, polyimide resin, and polycarbonate resin are preferable from the viewpoint of uniform dispersion of the resin composition for master batch.
Example
[0077]
　Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
[Evaluation Method] In the following
　Examples and Comparative Examples, the physical characteristics of the ethylene / α-olefin copolymer were measured by the following methods.
Absorption around
　721 cm -1 based on rolling vibration of long-chain methylene group using Fourier transform infrared spectrophotometer FT / IR-610 or FT / IR-6100 manufactured by JASCO Corporation. Calculate the absorbance ratio (D1155cm -1 / D721cm -1 ) with absorption near 1155cm -1 based on the skeletal vibration of propylene, and prepare a calibration line in advance (created using the standard sample at ASTM D3900). The ethylene content (% by mass) based on the mass was determined. Next, using the obtained ethylene content (mass%), the molar ethylene content (mol%) was determined according to the following formula.
[0078]
[Number 1]

[0079]
　　 The
　molecular weight distribution was measured using HLC-8320GPC of Tosoh Corporation as follows. As a separation column, TSKgel SuperMultipore HZ-M (4 pieces) was used, the column temperature was 40 ° C., tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the mobile phase, the developing speed was 0.35 ml / min, and the sample concentration was set to 0.35 ml / min. The sample injection volume was 5.5 g / L, the sample injection volume 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. According to the general-purpose calibration procedure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, and the molecular weight distribution (Mw / Mn) was calculated from these values.
[0080]

　The kinematic viscosity at 100 ° C. was measured and calculated by the method described in JIS K2283.
[0081]
Using
　o-dichlorobenzene-d4 as a measurement solvent, under 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). Then, 1 H-NMR spectrum (400 MHz, JEOL ECX400P) was measured. A solvent peak (orthodichlorobenzene 7.1 ppm) was used as the chemical shift criterion, derived from the main peak observed at 0 to 3 ppm and vinyl, vinylidene, disubstituted olefins and trisubstituted olefins observed at 4 to 6 ppm. The amount of unsaturated bonds per 1000 carbon atoms (pieces / 1000C) was calculated from the ratio of the integrated values ​​of the peaks.
[0082]
In the
　cutting, the molten strand after melting and mixing by the extruder was evaluated as "possible" when it was possible to cut it by the pelletizer for the extruder, and as "impossible" when it was not possible.
[0083]

　Stickiness is defined as "yes" when oily substances are deposited by visual inspection and tactile evaluation of the obtained pellets, and "no" when oily substances are not deposited. Evaluated as.
[0084]
The appearance after heating the
　obtained molded product to 120 ° C. for the polyamide resin molded product and 100 ° C. for the thermoplastic polyester resin molded product in an oven in the air and holding it for 168 hours is evaluated. bottom. The notation of the result is as follows.
◯: No change in surface appearance
×: Oily substance deposited on the surface of the molded product
[0085]
The
　Charpy impact strength was measured using a notched multipurpose test piece in accordance with ISO-179.
[0086]
The
　friction coefficient and specific wear amount were measured using a Matsubara-type friction and wear tester in accordance with JIS K 7218 "Plastic slip wear test method A". The test conditions were mating material: S45C, speed: 50 cm / sec, distance: 3 km, load: 15 kg (coefficient of friction) or 2.5 kg (specific wear amount), measurement environment temperature: 23 ° C., 150 ° C. When the test piece penetrated due to wear, the specific wear amount was described as> 10,000 × 10 -3 mm 3 / kgf · km.
[0087]
The
　limit PV value was evaluated by the stepwise method [JIS K7218 (SUS ring / resin sheet)]. Specifically, the sliding speed is 0.2 m / s, the test load is 0.25 to 25 MPa (steps every 0.25 MPa), and the test temperature is 23 ° C. The limit PV value was calculated from the test load and sliding speed until the friction coefficient 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: Polypropylene-poly (ethylene / butylene)- Polypropylene block copolymer, Septon ™ 8007L manufactured by Kuraray Co., Ltd. (styrene content: 30% by weight, MFR 230 ° C.: 2 g / 10 minutes, copolymer Mw: 90,000)
[(b) Polypropylene resin ]
　PP: Made by Prime Polymer Co., Ltd., Prime Polypro Co., Ltd. F107 (MFR230 ° C.: 7 g / 10 minutes)
[(c) Production of ethylene / α-olefin copolymer]
　(c) Ethylene / α-olefin copolymer weight The coalescence was produced by the following method.
[0088]

Synthesis Example 1]
[methylphenylmethylene (eta 5 - cyclopentadienyl) (eta 5 Synthesis of 2,7--t- butyl fluorenyl) zirconium dichloride
(i) 6
　Under the synthetic nitrogen atmosphere of -methyl-6- phenylfulvene, 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 obtained solution was cooled in an ice bath, and 15.0 g (111.8 mmol) of acetophenone was added dropwise. Then, the mixture was stirred at room temperature for 20 hours, and the obtained solution was quenched with a dilute aqueous hydrochloric acid solution. 10 mL of hexane was added to this solution to extract the soluble component, and the organic layer was washed with water and saturated brine, and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off, and the obtained viscous liquid was separated by column chromatography (hexane) to obtain the target product, 6-methyl-6-phenylfulvene (red viscous liquid).
[0089]
(Ii) Synthesis of methyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane
　Under a nitrogen atmosphere, 2,7-di-t-butylfluorene in a 100 mL three-necked flask. 01 g (7.20 mmol) and 50 mL of dehydrated 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 in 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-phenylfluven, the mixture was stirred under heating under reflux for 1 hour. 50 mL of water was gradually added while cooling in an ice bath, and the resulting two-layer 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 3 times with 50 mL of water and once with 50 mL of saturated brine. The organic layer was dried over anhydrous magnesium sulfate for 30 minutes, and then the solvent was distilled off under reduced pressure. When a small amount of hexane was added and ultrasonic waves were applied to the obtained solution, a solid was precipitated. Therefore, this was collected and washed with a small amount of hexane. This solid was dried under reduced pressure to obtain 2.83 g of methyl (cyclopentadienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane as a white solid.
[0090]
(Iii) [methylphenylmethylene (eta 5 - cyclopentadienyl) (eta 5 -2,7-di -t- butyl-fluorenyl) Synthesis of zirconium dichloride
　under a nitrogen atmosphere, methyl (cyclopenta in 100mL Schlenk tube 1.50 g (3.36 mmol) of dienyl) (2,7-di-t-butylfluorenyl) (phenyl) methane, 50 mL of dehydrated toluene and 570 μL (7.03 mmol) of THF were added in sequence. 4.20 mL (6.93 mmol) of n-butyllithium / hexane solution (1.65 M) was gradually added while cooling in 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 prepare a red solution. 728 mg (3.12 mmol) of zirconium tetrachloride was added while cooling in a methanol / dry ice bath, and the mixture was stirred for 16 hours while gradually raising the temperature to room temperature to obtain a red-orange slurry. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. After distilling off the solvent under reduced pressure and concentrating, a small amount of hexane was added and left at −20 ° C. to precipitate a red-orange solid. After washing the solid with a small amount of hexane, and dried under reduced pressure, as a red-orange solid [methylphenylmethylene (eta 5 - cyclopentadienyl) (eta 5 -2,7-di -t- Buchirufuru Olenyl)] 1.20 g of zirconium dichloride was obtained.
[0091]

　710 mL of heptane and 145 g of propylene were charged into a stainless steel autoclave having an internal volume of 2 L sufficiently substituted with nitrogen, and after raising the temperature in the system to 150 ° C., hydrogen 0.40 MPa and ethylene 0.27 MPa The total pressure was adjusted to 3 MPaG. Then triisobutylaluminum 0.4 mmol, [methylphenylmethylene (eta 5 - cyclopentadienyl) (eta 5 -2,7-di -t- butyl-fluorenyl)] zirconium dichloride 0.0001mmol and N, N- Polymerization was started by press-fitting 0.001 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate with nitrogen and setting the stirring speed to 400 rpm. Then, by continuously supplying only ethylene, the total pressure was maintained at 3 MPaG, and polymerization was carried out at 150 ° C. for 5 minutes. After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene, and hydrogen were purged. The obtained polymer solution was washed 3 times with 1000 mL of 0.2 mol / L hydrochloric acid and then 3 times with 1000 mL of distilled water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
[0092]
　Further, a polymer dissolved in 100 mL of a hexane solution of 0.5 mass% Pd / alumina catalyst and 500 mL of hexane was added to a stainless steel autoclave having an internal volume of 1 L, the autoclave was sealed, and then nitrogen substitution was performed. Then, the temperature was raised to 140 ° C. with stirring, the inside of the system was replaced with hydrogen, the pressure was increased to 1.5 MPa with hydrogen, and a hydrogenation reaction was carried out for 15 minutes.
[0093]
　The solvent of the obtained polymer solution was evaporated under reduced pressure and then dried under reduced pressure at 80 ° C. overnight to obtain 52.2 g of an ethylene-propylene copolymer (polymer 1). The content of the ethylene-derived structural unit of the polymer 1 was 53.1 mol%, the molecular weight distribution (Mw / Mn) was 1.8, and the kinematic viscosity at 100 ° C. was 605 mm 2 / s. The amount of unsaturated bonds in the polymer 1 was less than 0.1 / 1000C.
[Engineering
Plastics] PA: polyamide resin, PA6, Toray Co. Amiran CM1007
PET: thermoplastic polyester resin, polyethylene terephthalate, Unitika Ltd. Unitika polyester resin SA-1206
[Mineral oil]
　paraffinic process oil (Idemitsu Kosan Diana Process Oil PW-380, manufactured by Co., Ltd., kinematic viscosity at 100 ° C.: 30 mm 2 / s)
[0094]
[Examples 1 to 3 and Comparative Examples 1 to 4] In
　Examples 1 to 3 and Comparative Examples 1 to 4, SEBS and PP are premixed in the mass ratios shown in Table 1, respectively. Then, a 15 mmφ biaxial screw extruder (L / D = 45) was used to melt and mix under cylinder temperature conditions of 230 to 250 ° C. At the time of this melt mixing, the polymer 1 heated to 100 ° C. using a plunger type metering pump is quantitatively fed from the vent port of the extruder so that the polymer 1 has the mass ratio shown in Table 1 to perform a masterbatch. A resin composition for use was prepared. Table 1 shows the masterbatch moldability by evaluating the cutting of the masterbatch pellets made of this resin composition for masterbatch, and the evaluation of the stickiness of the obtained pellets.
　The numerical values ​​shown for SEBS, PP and polymer 1 in Table 1 indicate parts by mass.
[0095]
[table 1]

[0096]
[Reference Example 1]
　Polymer 1 in which PP is melted under a cylinder temperature condition of 280 ° C. using a biaxial screw extruder (L / D = 45) of 15 mmφ and heated to 100 ° C. using a plunger type metering pump. An attempt was made to prepare a masterbatch by quantitatively feeding the mixture from the vent port of the extruder. Although pellets were obtained up to 10 parts by mass of the polymer 1 added to 100 parts by mass of PP, 10 mass by mass was obtained. When the amount exceeded the portion, the discharge amount of the molten strand became unstable, and pellets could not be obtained. The pellet obtained by adding 10 parts by mass of the polymer 1 to 100 parts by mass of PP was designated as MB-R1.
[0097]
[Reference Example 2] Using
　PET as a base resin for a masterbatch, melting it under a cylinder temperature condition of 280 ° C. using a 15 mmφ biaxial screw extruder (L / D = 45), and using a plunger type metering pump. An attempt was made to prepare a masterbatch by quantitatively feeding polymer 1 heated to 100 ° C. from the vent port of the extruder, but pellets were added up to 5 parts by mass of polymer 1 with respect to 100 parts by mass of PET. However, when it exceeded 5 parts by mass, the discharge amount of the molten strand became unstable, and pellets could not be obtained. The pellet obtained by adding 5 parts by mass of the polymer 1 to 100 parts by mass of PET was designated as MB-R2.
[0098]
[Example 4, Example 5] The
　masterbatch pellets (MB) and PA obtained in Example 2 are premixed in the mass ratio shown in Table 2, and the cylinder temperature is 240 ° C. using the above-mentioned extruder. Pellets were prepared by melting and mixing under the conditions. Molded pieces are produced from the obtained pellets by injection molding, and the obtained molded pieces have appearance (appearance after heat aging), mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance. (Specific wear amount, limit PV value) was evaluated. The results are shown in Table 2.
[0099]
[Examples 6 and 7] The
　masterbatch pellets (MB) and PET obtained in Example 2 are premixed in the mass ratios shown in Table 2, and the cylinder temperature is 280 ° C. using the above-mentioned extruder. Pellets were prepared by melting and mixing under the conditions of. Molded pieces are produced from the obtained pellets by injection molding, and have appearance (appearance after heat aging), mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance (specific wear amount, limit PV value). ) Was evaluated. The results are shown in Table 2.
[0100]
[Comparative Example 5] The same
　procedure as in Example 4 was carried out except that the masterbatch pellet (MB) obtained in Example 2 was not used, and the obtained molded piece had an appearance (appearance after heat aging). , Mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance (specific wear amount, limit PV value) were evaluated. The results are shown in Table 3.
[0101]
[Comparative Example 6] The same
　procedure as in Example 6 was carried out except that the masterbatch pellet (MB) obtained in Example 2 was not used, and the obtained molded piece had an appearance (appearance after heat aging). , Mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance (specific wear amount, limit PV value) were evaluated. The results are shown in Table 3.
[0102]
[Comparative Example 7]
　A molded piece obtained in the same manner as in Example 4 except that 5 parts by mass of MB-R1 was used instead of 5 parts by mass of the masterbatch pellet (MB) obtained in Example 2. 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. The results are shown in Table 3.
[0103]
[Comparative Example 8]
　A molded piece obtained in the same manner as in Example 6 except that 6 parts by mass of MB-R2 was used instead of 6 parts by mass of the masterbatch pellet (MB) obtained in Example 2. 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. The results are shown in Table 3.
[0104]
[Comparative Example 9] The
　PA pellets are prepared by blending the polymer 1 and PA heated to 100 ° C. using a plunger type metering pump in the mass ratio shown in Table 4 and feeding them quantitatively from the vent port of the extruder. Made. A molded piece is produced from the obtained pellets by injection molding, and the obtained molded piece has an appearance (appearance after heat aging), mechanical properties (impact strength), slidability (coefficient of friction), and wear resistance (abrasion resistance). The specific wear amount and the limit PV value) were evaluated. The results are shown in Table 4.
[0105]
[Comparative Example 10] The same
　procedure as in Comparative Example 9 was carried out except that 2 parts by mass of mineral oil was used instead of 1 2 parts by mass of the polymer. Physical properties (impact strength), slidability (coefficient of friction), and wear resistance (specific wear amount, limit PV value) were evaluated. The results are shown in Table 4.
　The numerical values ​​shown for PA, PET, MB, MB-R1, MB-R2, polymer 1 and mineral oil in Tables 2 to 4 indicate parts by mass.
[0106]
[Table 2]

[0107]
[Table 3]

[0108]
[Table 4]

[0109]
　As shown in Table 1, in Examples 1 to 3 of the resin composition for masterbatch of the present invention, good pellets with excellent handling were obtained. The cutting speed of the pelletizer was adjusted so that the average particle size of the pellets was 3 to 4 mm. On the other hand, in (b) Comparative Example 1 containing no polyolefin resin and Comparative Example 2 having a low content, poor cutting of the molten strand occurred and pellets could not be obtained. Further, in Comparative Example 3 in which the content of (c) ethylene / α-olefin copolymer is excessive and in Comparative Example 4 in which the content of the polyolefin resin is excessive, (c) is obtained from the obtained pellets. The ethylene / α-olefin copolymer bleeded out, making it difficult to handle the pellets.
[0110]
　As shown in Tables 2 and 3, Examples 4 to 7, which are engineering plastic molded articles obtained by using the masterbatch obtained by the present invention, do not contain the resin composition for the masterbatch of the present invention. Compared with Comparative Example 5 and Comparative Example 6, all engineering plastics had excellent slidability and abrasion resistance.
[0111]
　Further, in Comparative Example 6 and Comparative Example 7 in which the pellets obtained in Reference Example 1 and Reference Example 2 were blended, a sufficient effect of improving slidability could not be obtained. In addition, if MB-R1 in which the olefin resin occupies most of the composition and MB-R2 that has undergone a thermal history due to melting and mixing are excessively blended, the conventional mechanical properties of engineering plastics may be significantly deteriorated. It is self-evident.
[0112]
　As shown in Table 4, in Comparative Example 9 and Comparative Example 10 in which the polymer 1 or mineral oil, which is an oil-like compound, was directly added to the engineering plastic, the oil-like compound bleeded out on the surface of the molded piece in a high temperature environment, and the appearance was changed. Was significantly inferior.
The scope of the claims
[Claim 1]
　(A) A block copolymer containing a polymer block mainly composed of a structural unit derived from a vinyl aromatic compound and a polymer block mainly composed of a structural unit derived from a conjugated diene compound, or a hydrogenated product thereof, and the hydrogenated product thereof. (A) 40 to 100 parts by mass of (b) polyolefin resin and 100 to 150 parts of (c) ethylene / α-olefin copolymer having the following characteristics (c1) to (c3) with respect to 100 parts by mass of the component. A resin composition for a master batch containing parts by mass.
(C1) The kinematic viscosity at 100 ° C. is 10 to 5,000 mm 2 / s
(c2) The content of structural units derived from ethylene is in the range of 30 to 85 mol%
(c3) Gel permeation chromatography The molecular weight distribution (Mw / Mn) is 2.5 or less in the molecular weight obtained by polystyrene conversion as measured by (GPC).
[Claim 2]
　The resin composition for a masterbatch according to claim 1, wherein the component (a) is a hydrogenated additive of the block copolymer.
[Claim 3]
　The resin composition for a masterbatch according to claim 1 or 2, wherein the kinematic viscosity of the ethylene / α-olefin copolymer (c) at 100 ° C. is 500 to 3,000 mm 2 / s.
[Claim 4]
　The resin composition for a masterbatch according to any one of claims 1 to 3, wherein the α-olefin of the ethylene / α-olefin copolymer (c) is propylene.
[Claim 5]
　The resin composition for a masterbatch according to any one of claims 1 to 4, wherein the polyolefin-based resin (b) is polypropylene.
[Claim 6]
　The resin composition for a masterbatch according to any one of claims 1 to 5, wherein the conjugated diene compound is butadiene.
[Claim 7]
　A pellet comprising the resin composition for masterbatch according to any one of claims 1 to 6, having an average particle size of more than 1 mm and 6 mm or less.
[Claim 8]
　The master batch resin composition according to any one of claims 1 to 6 with respect to any one of a polyacetal resin, an ABS resin, a polyamide resin, a thermoplastic polyester resin, a polyimide resin and a polycarbonate resin, and 100 parts by mass of the resin. A molded product containing 0.5 to 10 parts by mass of the product.
[Claim 9]
Mainly composed 　of any one of polyacetal resin, ABS resin, polyamide resin, thermoplastic polyester resin, polyimide resin and polycarbonate resin,
　and
(a) structural unit derived from vinyl aromatic compound with respect to 100 parts by mass of the resin. 0.2 to 3 parts by mass of a block copolymer or a hydrogenated product thereof containing a polymer block mainly composed of a structural unit derived from a polymer block and a conjugated diene compound, and
(b) a polyolefin resin 0.08 to 0.08 to 3 parts by mass and
(c) 0.2 to 4.5 parts by mass of an ethylene / α-olefin copolymer having the characteristics of (c1) to (c3)
　above, per 100 parts by mass of the component (a). The resin composition in which the content of the component (b) is 40 to 100 parts by mass and the content of the component (c) is 100 to 150 parts by mass.
[Claim 10]
　A molded product containing the resin composition according to claim 9.