JP6890432B2 - Composition for paddy roll and paddy roll - Google Patents

Description

The present invention relates to a composition for a paddy roll having abrasion resistance and excellent low temperature characteristics, and a paddy roll having the composition on its surface.

Ethylene-propylene copolymer (hereinafter sometimes referred to as EPR) and ethylene-propylene-non-conjugated diene copolymer (hereinafter sometimes referred to as EPDM) have weather resistance, ozone resistance, and chemical resistance. It is used for industrial rolls and office equipment rolls because it has excellent properties such as electrical insulation. By the way, it is desired that these rolls maintain the physical properties of the copolymer composition for a long period of time and are resistant to environmental deterioration.

Patent Document 1 proposes to improve the wear resistance of a roll by blending an ethylene / α-olefin / polyene amorphous copolymer with an organic peroxide, an organopolysiloxane, or the like. ..
However, it was found that when the roll obtained from the composition disclosed in Patent Document 1 was used for the paddy roll, the wear resistance was still insufficient.

Japanese Unexamined Patent Publication No. 11-323043

An object of the present invention is to obtain a composition suitable for a paddy roll having abrasion resistance and excellent low temperature characteristics, and a paddy roll having the composition on the surface.

As a result of diligent research to solve the above problems, the present inventors have grafted an unsaturated carboxylic acid or a derivative thereof on an ethylene / α-olefin / non-conjugated polyene copolymer together with a specific filler. An α-olefin copolymer, preferably a more specific silylated polyolefin and / or a derivative thereof (however, a silicon-containing compound represented by the formula (1) described later and having two or more SiH groups in one molecule. A vinyl group-containing compound having a number average molecular weight (Mn) of 100 or more and 500,000 or less and having an average of 2.0 or more vinyl groups per molecule as measured by gel permeation chromatography (GPC). The dispersibility of the filler can be improved by blending (excluding the silylated polyolefin which is the reaction product of the above) and its derivatives), thereby improving the moldability. Therefore, a copolymer composition layer having excellent wear resistance is preferable. It was found that by using the copolymer composition layer on the surface of the paddy roll, the paddy roll having excellent wear resistance and durability can be used for a long period of time, and the present invention has been completed. It was.

That is, the present invention provides an invention relating to a paddy roll having a copolymer composition layer on the surface, and the copolymer composition layer has the following characteristics.
Ethylene, α-olefin with 4 to 20 carbon atoms, non-conjugated polyene copolymer (A), 100 parts by mass,
A graft-modified ethylene / α-olefin copolymer (B) grafted with an unsaturated carboxylic acid or a derivative thereof (B) 0.1 to 10 parts by mass, and a filler (C) satisfying the following requirement (C-1) (however, carbon A paddy roll comprising a copolymer composition containing 1 to 100 parts by mass (excluding black).
(C-1) The average particle size is 10 μm to 50 μm.

According to the present invention, the composition for paddy rolls of the present invention has a graft-modified ethylene / α-olefin copolymer weight obtained by grafting an ethylene / α-olefin / non-conjugated polyene copolymer component with an unsaturated carboxylic acid or a derivative thereof. By blending the coalescence and a specific silylated polyolefin and / or a derivative thereof, which are optional components, together with the filler, the dispersibility of the filler can be improved and the abrasion resistance is very excellent, so that the filler can be used for a long period of time. It is possible to provide a paddy roll having a layer on the surface thereof.

<Ethylene / α-olefin / non-conjugated polyene copolymer (A)>
Ethylene / α-olefin / non-conjugated polyene copolymer (A), which is one of the components contained in the copolymer composition according to the present invention [hereinafter, may be referred to as “copolymer (A)”. .. ] Is a copolymer containing a structural unit derived from ethylene, a structural unit derived from an α-olefin having 4 or more carbon atoms, preferably 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention may be used alone or in combination of two or more. The copolymer (A) is not limited to structural isomers such as trans isomers and cis isomers as long as the effects of the present invention are exhibited.

Specific examples of the α-olefin having 4 or more carbon atoms include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-. Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonene, 1-eicosene, 9-methyl-1-decene, 14-methyl-1-dodecene and Examples thereof include 12-ethyl-1-tetradecene. Of these, α-olefins having 4 to 10 carbon atoms are preferable, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are more preferable, and 1-butene is particularly preferable.

These α-olefins may be used alone or in combination of two or more.
Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5. -Chain non-conjugated diene such as dimethyl-1,4-hexadiene, 7-methyl-1,6-octadien, 8-methyl-4-ethylidene-1,7-norbornene and 4-ethylidene-1,7-undecadien; Methyltetrahydroinden, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyriden-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene , 5-Vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene and cyclic non-conjugated diene such as norbornene; 2,3-diisopropylidene-5-norbornene, 2 -Etilidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornene, 4-ethylidene-8-methyl-1,7-nonadien and other trienes can be mentioned. Of these, a mixture of 1,4-hexadien, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene is preferable, and 5-ethylidene-2 is preferable. A mixture of -norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene is more preferred.

These non-conjugated polyenes may be used alone or in combination of two or more.
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention preferably satisfies the following requirements (A-1) to (A-3).

(A-1)
A constitution derived from α-olefin having 4 or more carbon atoms and containing a structural unit derived from ethylene in an amount of more than 70% by mass and 99% by mass or less, preferably 70 to 90% by mass, more preferably 70 to 85% by mass. The unit is contained in an amount of 1% by mass or more and less than 30% by mass, preferably 10 to 30% by mass, more preferably 15 to 30% by mass [however, the sum of the structural units derived from ethylene and the structural units derived from α-olefin. The amount is 100% by mass. ].

The structural unit derived from the non-conjugated polyene is usually 1.0 to 20.0 parts by mass, preferably 1.0 to 20.0 parts by mass, based on 100 parts by mass of the total amount of the structural unit derived from ethylene and the structural unit derived from α-olefin. It is contained in an amount of 3.0 to 15.0 parts by mass, more preferably 4.0 to 14.0 parts by mass.

The composition of the ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention ^{can be measured using, for example, 13} C-NMR or the like in accordance with ASTM D 3900 and ASTM D 6047.

(A-2)
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has a Mooney viscosity ML _{(1 + 4)} (100 ° C.) at 100 ° C. obtained by measuring according to ASTM D 1646. , 1-90, more preferably 1-60, even more preferably 1-30. When the Mooney viscosity is in the above range, it is preferable because it exhibits good processability and good physical characteristics.

(A-3)
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention has an ultimate viscosity [η] measured in decalin at 135 ° C. of 1.0 to 5.0 dl / g, preferably 1. It is .0 to 4.0 dl / g.

<Method for producing ethylene / α-olefin / non-conjugated polyene copolymer (A)>
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention can be produced by using a known polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. The polymerization method is not particularly limited, and can be carried out by a liquid phase polymerization method such as solution polymerization, suspension polymerization, bulk polymerization method, gas phase polymerization method, or other known polymerization method. Further, these copolymers are not limited as long as the effects of the present invention are exhibited, and are also available as commercial products. Examples of commercially available products include Vistalon (registered trademark) manufactured by ExxonMobil, Esplen (registered trademark) manufactured by Sumitomo Chemicals, Inc., and Mitsui EPT (registered trademark) manufactured by Mitsui Chemicals, Inc.

<Graft-modified ethylene / α-olefin copolymer (B) grafted with unsaturated carboxylic acid or its derivative>
A graft-modified ethylene / α-olefin copolymer (B) grafted with an unsaturated carboxylic acid or a derivative thereof, which is one of the components contained in the copolymer composition according to the present invention [hereinafter, "modified copolymer". It may be abbreviated as "(B)". ], The amount of the unsaturated carboxylic acid or its derivative grafted is usually 0.1 to 10% by mass, preferably 1 to 10% by mass, more preferably 1 to 10% by mass, based on 100% by mass of the modified copolymer (B). Is 2-9% by mass.

Modified copolymer (B) according to the present invention is preferably has a density, 860 kg / m ³ or more 880 kg / m less than ^3, more preferably 860~875kg / m ^3, more preferably at 865~875kg / m ³ is there. When the density of the modified copolymer (B) is within the above range, the paddy roll obtained from the copolymer composition according to the present invention has an excellent balance between flexibility and physical properties.

The modified copolymer (B) according to the present invention has a melting point measured by differential scanning calorimetry (DSC) of 20 ° C. or higher and lower than 60 ° C., or has a peak indicating a melting point by differential scanning calorimetry (DSC). It is preferably not observed. When the modified copolymer (B) satisfies this condition, the dispersibility in the copolymer (A) at the time of kneading molding is excellent. When a peak indicating a melting point is observed by differential scanning calorimetry (DSC), the melting point is more preferably 30 ° C. or higher and lower than 60 ° C., and further preferably 40 ° C. or higher and lower than 60 ° C.

The unsaturated carboxylic acid and / or a derivative thereof according to the present invention has one or more unsaturated compounds having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, or one or more anhydrous carboxylic acid groups. Unsaturated compounds and the like can be mentioned, and examples of the unsaturated group include a vinyl group, a vinylene group, an unsaturated cyclic hydrocarbon group and the like. Specific compounds include, for example, acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endosys-bicyclo [2.2.1]. Unsaturated carboxylic acids such as hepto-5-ene-2,3-dicarboxylic acid); or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters and the like. Specific examples of such derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. These unsaturated carboxylic acids and / or derivatives thereof may be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferable. The content of the unsaturated carboxylic acid and / or its derivative can be easily controlled, for example, by appropriately selecting the graft conditions.

The method for grafting a graft monomer selected from an unsaturated carboxylic acid and / or a derivative thereof to an ethylene / α-olefin copolymer is not particularly limited, and conventionally known graft polymerization methods such as a solution method and a melt-kneading method can be used. Can be adopted. For example, a method in which an ethylene / α-olefin copolymer is melted and a graft monomer is added thereto to cause a graft reaction, or an ethylene / α-olefin copolymer is dissolved in a solvent to form a solution and grafted therein. There is a method of adding a polymer to cause a graft reaction.

In these methods, when graft polymerization is carried out in the presence of a radical initiator, the graft monomer such as the unsaturated carboxylic acid can be efficiently graft-polymerized. In this case, the radical initiator is usually used in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer.

As such a radical initiator, an organic peroxide, an azo compound or the like is used. As such a radical initiator, an organic peroxide, an azo compound or the like is used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di (peroxide benzoate) hexin-. 3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butyl peroxide) hexin-3,2,5 -Dimethyl-2,5-di (t-butyl peroxide) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octate, t-butylperpi Valate, cumylperpivalate, t-butylperdiethyl acetate; azobisisobutyronitrile, dimethylazoisobutyrate and the like.

Of these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (t) Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.

The reaction temperature of the graft polymerization reaction using a radical initiator or the graft polymerization reaction performed without using a radical initiator is usually set in the range of 60 to 350 ° C., preferably 150 to 300 ° C.

The ethylene / α-olefin copolymer used in the production of the modified copolymer (B) according to the present invention contains a unit derived from ethylene and an α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms. It is a copolymer containing a unit derived from, and may be a random copolymer or a block copolymer.

Specific examples of the α-olefin include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1 -Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl -1-Tetradecene and the like can be mentioned. Of these, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.

The content of the structural unit derived from ethylene in the ethylene / α-olefin copolymer according to the present invention is usually 50.0 mol% or more 100 with respect to all the structural units contained in the ethylene / α-olefin copolymer. It is less than mol%, preferably 80.0 to 99.5 mol%, more preferably 90.0 to 99.0 mol%.

The density of the ethylene / α-olefin copolymer according to the present invention is such that the density of the graft-modified ethylene / α-olefin copolymer (B) obtained by graft-modifying the copolymer is within the above range. It is preferably 850 to 880 kg / m ³ , and more preferably 855 to 875 kg / m ³ .

The melting point of the ethylene / α-olefin copolymer according to the present invention is such that the melting point of the graft-modified ethylene / α-olefin copolymer (B) obtained by graft-modifying it satisfies the above conditions. More specifically, the melting point measured by differential scanning calorimetry (DSC) is 20 to 70 ° C., or no peak indicating the melting point is observed by differential scanning calorimetry (DSC). Preferably, the melting point measured by differential scanning calorimetry (DSC) is 30-60 ° C., or no peak indicating the melting point is observed by differential scanning calorimetry (DSC).

The melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.16 kg load) of the ethylene / α-olefin copolymer according to the present invention is preferably 0.1 to 100 g / 10 minutes, more preferably 0.2. ~ 50 g / 10 minutes, more preferably 0.3 to 20 g / 10 minutes.

When a copolymer (B) obtained by graft-modifying an ethylene / α-olefin copolymer having a density, an ethylene content and an MFR in the above ranges is used, the balance between the processability of the composition and the rubber elasticity is good. become.

<Filler (C)>
The filler (C), which is one of the components contained in the copolymer composition according to the present invention, has the following requirements, unlike carbon black such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT. As long as (C-1) is satisfied, those usually used as a reinforcing material for synthetic rubber can be used.

(C-1)
The filler (C) according to the present invention has an average particle size of usually 10 to 50 μm, preferably 20 to 40 μm for the reason of balance between dispersibility and physical properties. In the present invention, the average particle size means a particle size d50 equivalent to 50% obtained from an integrated distribution curve measured using a laser diffraction type particle size distribution measuring device (particle size distribution measuring device based on a laser diffraction / scattering method). ..

Examples of the filler (C) according to the present invention include silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine powder talc, fine powder silicic acid, talc, clay, calcium silicate, kaolin, talc, keiso soil, and mica. Powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass bulb, silas balloon, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker Or, the surface of these inorganic substances treated with a silane coupling agent or the like can be used. Considering the use of grain removal of rice, it is not preferable to use a filler having a black color or color such as carbon black, and a filler having a white color such as silica, activated calcium carbonate, light calcium carbonate, or heavy calcium carbonate is preferable. preferable. Among these, silica is more preferable from the viewpoints of being able to obtain excellent dispersibility, being able to obtain carbon black and wear resistance of identification degree, and improving rigidity.
The filler (C) according to the present invention preferably further has the following requirement (C-2).

(C-2)
The specific surface area of the filler (C) according to the present invention is not particularly limited as long as the effects of the present invention are exhibited, but it is usually preferably ^{5 to} 120 m 2 / g.

<Copolymer composition for paddy roll>
Copolymer composition for paddy roll according to the present invention [Hereinafter, it may be referred to as "copolymer composition". ] Is preferably 0.01 to 50 parts by mass of the modified copolymer (B) with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (A) having 4 to 20 carbon atoms. Is 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, and the filler (C) is 1 to 100 parts by mass, preferably 30 to 100 parts by mass, more preferably high hardness. It contains 40 to 100 parts by mass.

By containing the modified copolymer (B) in the copolymer composition according to the present invention, a paddy roll having excellent wear resistance can be obtained.
The copolymer composition according to the present invention is added to the above ethylene / α-olefin / non-conjugated polyene copolymer (A) having 4 to 20 carbon atoms, the above modified copolymer (B) and the above filler (C). , Cyrilized polyolefin and / or its derivative (D) (However, the silicon-containing compound having two or more SiH groups in one molecule as the silicon-containing compound, and an average of 2.0 per molecule as the vinyl group-containing compound. It may contain (excluding silylated polyolefin, which is a reaction product with the above vinyl group-containing compound having a vinyl group, and a derivative thereof).

When the copolymer composition according to the present invention contains the above-mentioned silylated polyolefin and / or its derivative (β), the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (A) 100 having 4 to 20 carbon atoms It is preferably in the range of 0.01 to 100 parts by mass, more preferably 1 to 20 parts by mass with respect to parts by mass.

<Cyrilized polyolefin and / or its derivative (D)>
Cyrilized polyolefin and / or its derivative (D) according to the present invention [hereinafter, may be abbreviated as "silylated polyolefin (D)". ] Is a silicon-containing compound containing a structural unit represented by the following formula (1) and a vinyl group having a number average molecular weight (Mn) of 100 or more and 500,000 or less as measured by gel permeation chromatography (GPC). It is a reaction product with the contained compound (however, the silicon-containing compound having two or more SiH groups in one molecule is used, and the vinyl group-containing compound has an average of 2.0 or more vinyl groups per molecule. That is, the silicon-containing compound has a silicon-containing compound having two or more SiH groups in one molecule, and the vinyl group-containing compound contains a vinyl group having an average of 2.0 or more vinyl groups per molecule. Cyrilized polyolefin, which is a reaction product with a compound, and its derivatives are excluded).

−Si (R ¹ ) ^{HY 1} − ··· (1)
In the above formula (1), R ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group, and Y ¹ is O.
S or NR ³⁰ (R ³⁰ is a hydrogen atom or hydrocarbon group).

The structure of the silylated polyolefin (D) according to the present invention is not clear, but for example, -Si-H in the silicon-containing compound containing the structural unit of the above formula (1) and -CH in the vinyl group-containing compound. = It is considered that it contains a -Si-CC- structure formed by reacting with _{CH 2 (vinyl group).} However, when a compound having two or more SiH groups in one molecule is used as the silicon-containing compound and a compound having an average of 2.0 or more vinyl groups per molecule is used as the vinyl group-containing compound, it is obtained. It is considered that the silylated polyolefin produced is likely to have, for example, a network structure, and such a case is excluded in the present embodiment.

The copolymer composition layer composed of the copolymer composition containing the silylated polyolefin (D) according to the present invention and the crosslinked product obtained by cross-linking the copolymer composition has an improved surface silicon concentration and a copolymer weight. The present inventors speculate that the surface free energy of the coalesced composition layer is suppressed and that the coalesced composition layer has good abrasion resistance.

Further, the silylated polyolefin (D) is a filler (C) because the silylated polyolefin is satisfactorily distributed in the copolymer composition layer as compared with conventional additives such as silicone-based additives and metal soaps. ) Can be satisfactorily prevented from falling off, and the silylated polyolefin has a hydrophobic bond with the filler (C), particularly ethylene, an α-olefin having 4 to 20 carbon atoms, and a non-conjugated polyene copolymer (A). Further, SiH and silica have a high affinity with silica because hydrogen bonds can be formed, and bleeding and blooming on the surface of the copolymer composition layer are unlikely to occur. Therefore, such a copolymer composition layer The present inventors presume that the paddy roll having a surface of the copolymer has good abrasion resistance and durability.

《Silicon-containing compound》
The silicon-containing compound constituting the silylated polyolefin (D) according to the present invention is a hydrosilane compound having a structural unit represented by the following formula (1).

−Si (R ¹ ) ^{HY 1} − ··· (1)
In the above formula (1), R ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group, and Y ¹ is O, S or NR ³⁰ (R ³⁰ is a hydrogen atom or a hydrocarbon group).

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
As the hydrocarbon group, a hydrocarbon group having 2 to 40 carbon atoms is preferable, and a hydrocarbon group having 2 to 20 carbon atoms is more preferable. Specific examples thereof include an alkyl group, an alkenyl group and an aryl group. In R ¹ and R ³⁰ , the hydrocarbon groups may be the same or different from each other.

Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group and an octadecyl group. Examples thereof include a linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a norbornyl group; an arylalkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group.

Examples of the alkenyl group include a vinyl group, a propenyl group, a cyclohexenyl group and the like.
Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a biphenyl group, a naphthyl group, a methylnaphthyl group, an anthryl group, a phenanthryl group and the like.

Further, the above-mentioned hydrocarbon group may contain one or more heteroatoms. Specifically, a group in which at least one hydrogen of these groups is replaced with a group containing a halogen atom, oxygen, nitrogen, silicon, phosphorus and sulfur can be mentioned.

In one embodiment, the silicon-containing compound has a structure represented by the formula (2).
^{R 22 - (Si (R 21} ) H-Y 21) m -Z- (Y 22 -Si (R 23) H) n -R 24 ··· (2)
In the above formula (2), R ²¹ and R ²³ are independently hydrogen atoms, halogen atoms or hydrocarbon groups, respectively.
R ²² and R ²⁴ are independent halogen atoms or hydrocarbon groups, respectively.
Y ²¹ and Y ²² are independently O, S or NR ³⁰ (R ³⁰ is a hydrogen atom or hydrocarbon group).
m is 0 or 1 and
n is 0 or 1
When ^{there are a plurality of R 21} , R ²³ , Y ²¹ and Y ²² , each group may be the same or different.
Z is a divalent group represented by the following formula (3):
−Si (R ⁴¹ ) (R ⁴¹ ) − (Y ²³ −Si (R ⁴¹ ) (R ⁴¹ )) _l − ・ ・ ・ (3)
In the above formula (3), R ⁴¹ is a hydrogen atom, a halogen atom or a hydrocarbon group, and each R ⁴¹ may be the same or different, and Y ²³ is independently O, S or NR ³⁰ (R ³⁰ is a hydrogen atom or hydrocarbon group)
l is an integer from 0 to 10,000.

However, in the above formula (2), when m = n = 0, at least one R ⁴¹ in the above formula (3) is a hydrogen atom.
The definitions of the halogen atom and the hydrocarbon group in the above formula (2) and the above formula (3) are the same as the definitions in the above formula (1).

Further, it is also a typical embodiment that the hydrocarbon group in the above formulas (1), (2) and (3) is composed of only a carbon atom and a hydrogen atom.
In one embodiment, the silicon-containing compound preferably has 3 or more, more preferably 5 or more, and even more preferably 10 or more silicon atoms. The silicon-containing compound preferably has 10,000 or less, more preferably 1,000 or less, particularly preferably 300 or less, and even more preferably 50 or less silicon atoms. By using the silylated polyolefin using such a silicon-containing compound, the silylated polyolefin (D) is satisfactorily unevenly distributed in the copolymer composition layer, and the filler (C) can be prevented from falling off, and the filler (C) can be prevented from falling off. Since bleeding and blooming on the surface of the copolymer composition layer are less likely to occur due to the good affinity with the filler (C), a copolymer composition layer having excellent scratch resistance and durability can be obtained. The scratch resistance referred to here includes wear resistance, abrasion resistance, and slidability.

In one embodiment, l in the above formula (3) is an integer of 0 to 10,000, but preferred upper and lower limits are the values of m and n in the above formula (2) and the preferred number of silicon atoms. You can list the number that is determined from.

In one embodiment, a silicon-containing compound having m = n = 1, that is, SiH groups at both ends in the above formula (2) is preferably used.
In one embodiment, a silicon-containing compound having m = 1 in the above formula (2) and n = 0, that is, a SiH group at one end, is preferably used.

Particularly preferable silicon-containing compounds include compounds in which m = n = 1 in the above formulas (2) and (3), and R ²¹ , R ²³ and R ⁴¹ are all hydrocarbon groups. The hydrocarbon groups may be the same or different.

As another particularly preferable silicon-containing compound, in the above formulas (2) and (3), m = 1, n = 0, and R ²¹ and R ⁴¹ are all hydrocarbon groups. The hydrocarbon groups may be the same or different.

Specific examples of the silicon-containing compound used in this embodiment are shown below. Examples of the silicon-containing compound of the present embodiment include compounds having one SiH group.
Examples of the silicon-containing compound having one SiH group include a compound represented by the following formula (2a), and a part or all of the methyl group in the formula (2a) is an ethyl group, a propyl group, a phenyl group, or a tri. Examples thereof include compounds substituted with a hydrocarbon group which may contain one or more heteroatoms such as a fluoropropyl group.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) d -Si (CH 3) 3 ··· (2a)
(In the above formula (2a), d is an integer of 1 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50).

More specific examples of such compounds include the following compounds, which are C ₄ H ₉ − ((CH ₃ ) ₂ SiO) ₉ − (CH ₃ ) ₂ SiH.
C ₄ H ₉ − ((CH ₃ ) ₂ SiO) ₆₅ − (CH ₃ ) ₂ SiH
As another example of the silicon-containing compound having one SiH group, for example, a dimethylsiloxane / methylhydrogensiloxane copolymer represented by the following formula (2b), a part of the methyl group in the following formula (2b), or Examples thereof include compounds in which all are substituted with a hydrocarbon group which may contain one or more heteroatoms such as an ethyl group, a propyl group, a phenyl group and a trifluoropropyl group.

Si (CH ₃ ) ₃ O- (-Si (CH ₃ ) _2- O-) _e -(-SiH (CH ₃ ) -O-)-Si (CH ₃ ) ₃ ... (2b)
(In the above formula (2b), e is an integer of 0 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50).

The order in which the -Si (CH ₃ ) _2- O- unit and the -SiH (CH ₃ ) -O- unit are arranged is not particularly limited, and is statistically random regardless of whether it is blocky or disordered. It may be.

More specific examples of such a compound include, but are not limited to, the compounds shown below.
Si (CH ₃ ) ₃ O-SiH (CH ₃ ) -O-Si (CH ₃ ) ₃
Examples of the silicon-containing compound of the present embodiment also include compounds having two or more SiH groups.

Examples of silicon-containing compounds having two or more SiH groups include methylhydrogenpolysiloxane represented by the following formula (2c), and part or all of the methyl groups in the following formula (2c) are ethyl groups and propyls. Examples thereof include compounds substituted with a hydrocarbon group which may contain one or more heteroatoms such as a group, a phenyl group and a trifluoropropyl group.

(CH ₃ ) ₃ SiO- (-SiH (CH ₃ ) -O-) _f- Si (CH ₃ ) ₃ ... (2c)
(In the above formula (2c), f is an integer of 2 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50).

As another example of the silicon-containing compound having two or more SiH groups, for example, a dimethylsiloxane / methylhydrogensiloxane copolymer represented by the following formula (2d), a part of the methyl group in the following formula (2d). Alternatively, a compound in which all of them are substituted with a hydrocarbon group which may contain one or more heteroatoms such as an ethyl group, a propyl group, a phenyl group and a trifluoropropyl group can be mentioned.

_{(CH 3) 3 SiO - (} - Si (CH 3) 2 -O-) g - (- SiH (CH 3) -O-) h -Si (CH 3) 3 ··· (2d)
(In the above formula (2d), g is an integer of 1 or more, h is an integer of 2 or more, and the upper limit of the total of g and h is, for example, 1000, preferably 300, and more preferably 50. ).

Further, in the above equation (2d), the order in which the −Si (CH ₃ ) ₂ −O− unit and the −SiH (CH ₃ ) −O− unit are arranged is not particularly limited, and even if it is block-like, it is disorderly. It may be statistically random.

More specific examples of such a compound include, but are not limited to, the compounds shown below.

ＳｉＨ基を２個以上有するケイ素含有化合物のさらに別の例としては、例えば、下記式（２ｅ）で表されるメチルハイドロジェンポリシロキサン、下記式（２ｅ）においてメチル基の一部または全部がエチル基、プロピル基、フェニル基、トリフロロプロピル基等の１つ以上のヘテロ原子を含んでいてもよい炭化水素基で置換された化合物等が挙げられる。

As yet another example of the silicon-containing compound having two or more SiH groups, for example, methylhydrogenpolysiloxane represented by the following formula (2e), and a part or all of the methyl groups in the following formula (2e) are ethyl. Examples thereof include compounds substituted with a hydrocarbon group which may contain one or more heteroatoms such as a group, a propyl group, a phenyl group and a trifluoropropyl group.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) i -Si (CH 3) 2 H ··· (2e)
(In the above formula (2e), i is an integer of 1 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50).

More specific examples of such a compound include, but are not limited to, the compounds shown below.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 5 -Si (CH 3) 2 H
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 8 -Si (CH 3) 2 H
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 18 -Si (CH 3) 2 H
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 80 -Si (CH 3) 2 H
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) 230 -Si (CH 3) 2 H
As yet another example of the silicon-containing compound having two or more SiH groups, for example, methylhydrogenpolysiloxane represented by the following formula (2f), and a part or all of the methyl groups in the following formula (2f) are ethyl. Examples thereof include compounds substituted with a hydrocarbon group which may contain one or more heteroatoms such as a group, a propyl group, a phenyl group and a trifluoropropyl group.

_{HSi (CH 3) 2 O -} (- SiH (CH 3) -O-) j -Si (CH 3) 2 H ··· (2f)
(In the above formula (2f), j is an integer of 1 or more, and the upper limit is, for example, 1000, preferably 300, and more preferably 50).

As yet another example of the silicon-containing compound having two or more SiH groups, for example, a dimethylsiloxane / methylhydrogensiloxane copolymer represented by the following formula (2 g), one of the methyl groups in the following formula (2 g). Examples thereof include compounds in which some or all of them are substituted with a hydrocarbon group which may contain one or more heteroatoms such as an ethyl group, a propyl group, a phenyl group and a trifluoropropyl group.

_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) k - (- SiH (CH 3) -O-) l -Si (CH 3) 2 H ··· (2g)
(In the above formula (2g), k and l are integers of 1 or more, respectively, and the upper limit of the total of k and l is, for example, 1000, preferably 300, and more preferably 50).

In addition, there is no particular limitation on the order in which the -Si (CH ₃ ) ₂ -O- units and the -SiH (CH ₃ ) -O- units are arranged, and they are statistically random regardless of whether they are blocky or disordered. It may be.

<< Vinyl group-containing compound >>
The vinyl group-containing compound constituting the silylated polyolefin (D) according to the present invention has a number average molecular weight (Mn) of 100 or more and 500,000 or less as measured by gel permeation chromatography (GPC), and is 100 or more and 100 or more. More preferably, it is 000 or less. When the number average molecular weight is at least the above lower limit value, it is possible to further suppress the bleeding and blooming of the obtained silylated polyolefin from the copolymer composition layer. When it is not more than the above upper limit value, the dispersibility of the silylated polyolefin in the copolymer composition layer is improved, and the handling of the copolymer composition layer becomes better. In this embodiment, as will be described later, the number average molecular weight (Mn), the weight average molecular weight (Mw), and Mw / Mn are polyethylene-equivalent values.

The vinyl group-containing compound according to the present invention will be described below.
The vinyl group-containing compound is obtained by polymerizing or copolymerizing one or more olefins usually selected from olefins having 2 to 50 carbon atoms.

Specific examples of the olefin having 2 to 50 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl. -1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1-pentene, 3,4-dimethyl-1 -Hexene, 4-methyl-1-hexene, 3,4-dimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinyl Α-olefins such as cyclohexane; olefins containing internal double bonds such as cis-2-butene, trans-2-butene, etc .; isobutene, 2-methyl-1-pentene, 2,4-dimethyl-1-pentene, 2, , 4-Dimethyl-1-hexene, 2,4,4-trimethyl-1-pentene, 2,4-dimethyl-1-hexene, 2-methyl-1-butene, 2-methyl-1-hexene, 2-methyl -1-Heptene, 2-methyl-1-octene, 2,3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,3-dimethyl-1 -Octen, 2,3,3-trimethyl-1-butene, 2,3,3-trimethyl-1-pentene, 2,3,3-trimethyl-1-hexene, 2,3,3-trimethyl-1-octene , 2,3,4-trimethyl-1-pentene, 2,3,4-trimethyl-1-hexene, 2,3,4-trimethyl-1-octene, 2,4,4-trimethyl-1-hexene, 2 , 4,4-trimethyl-1-octene, 2-methyl-3-cyclohexyl-1-propylene, vinylidenecyclopentane, vinylidenecyclohexane, vinylidenecyclooctane, 2-methylvinylidenecyclopentane, 3-methylvinylidenecyclopentane, 4- Vinylidene compounds such as methylvinylidenecyclopentane; aryls such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like. Vinyl compounds; arylvinylidene compounds such as α-methylstyrene, α-ethylstyrene, 2-methyl-3-phenylpropylene; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, metac Functional group-substituted vinylidene compounds such as -n-butyl glycolylate, isobutyl methacrylate, -tert-butyl methacrylate, 2-cyanopropylene, 2-aminopropylene, 2-hydroxymethylpropylene, 2-fluoropropylene and 2-chloropropylene. Cyclobutene, cyclopentene, 1-methyl-1-cyclopentene, 3-methyl-1-cyclopentene, 2-methyl-1-cyclopentene, cyclohexene, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, 2-methyl -1-Cyclohexene, cyclopentene, cyclooctene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 5,6-dihydrodicyclopentadiene, 3a, 4,5,6,7,7a-hexahydro-1H inden , Tricyclo [6.2.1.0 ^2,7 ] An aliphatic cyclic olefin containing internal double bonds such as undeca-4-ene, cyclopentadiene, dicyclopentadiene; cyclopenta-2-enylbenzene, cyclopenta-3-3 Fragrances such as enylbenzene, cyclohex-2-enylbenzene, cyclohexa-3-enylbenzene, inden, 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, 1,4-methino 1,4,4a, 9a tetrahydrofluorene Ring-containing cyclic olefins; butadiene, isoprene, 4-methyl-1,3-pentadiene, 4-methyl-1,4-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1 , 4-Hexadiene, 1,3-Hexadiene, 1,3-octadien, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, etilidennorbornene, vinylnorbornene, dicyclopentadiene , 7-Methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-norbornene, 5,9-dimethyl-1,4,8-decatorene, etc. Examples include cyclic polyene and chain polyene having two or more double bonds.

Further, the olefin having 2 to 50 carbon atoms may have a functional group containing atoms such as oxygen, nitrogen and sulfur. For example, unsaturated carboxylic acids such as acrylic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic acid and their sodium salts, potassium salts, lithium salts and zinc salts. , Magnesium salt, calcium salt and other unsaturated carboxylic acid metal salts; maleic anhydride, itaconic acid anhydride, bicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic acid anhydride and other unsaturated carboxylic acids. Acid anhydrides; methyl acrylate, ethyl acrylate, -n-propyl acrylate, isopropyl acrylate, -n-butyl acrylate, isobutyl acrylate, -tert-butyl acrylate, -2-ethylhexyl acrylate, etc. Unsaturated carboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, monoitaconate Unsaturated glycidyl esters such as glycidyl esters; halogenated olefins such as vinyl chloride, vinyl fluoride, allyl fluoride; unsaturated cyano compounds such as acryliconitrile, 2-cyano-bicyclo [2.2.1] hepta-5-ene Unsaturated ether compounds such as methyl vinyl ether and ethyl vinyl ether; unsaturated amides such as acrylamide, methacrylic acid and N, N-dimethylacrylamide; methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy Functional group-containing styrene derivatives such as styrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene; N-vinylpyrrolidone and the like can be mentioned.

In a preferred embodiment, the vinyl group-containing compound has a structure represented by the following formula (4) and has a number average molecular weight of 100 or more and 500,000 or less.
A-CH = CH ₂ ... (4)
Here, in the above formula (4), A is a polymerized chain containing one or more kinds of structural units derived from α-olefins having 2 to 50 carbon atoms.

In the above formula (4), preferably, the A part of the vinyl group-containing compound is a copolymer of two or more kinds of olefins selected from the group consisting of an ethylene polymer chain, a propylene polymer chain, or an α-olefin having 2 to 50 carbon atoms. It is a polymerized chain. The α-olefin is preferably an α-olefin having 2 to 20 carbon atoms.

In a preferred embodiment, A of the vinyl group-containing compound represented by the above formula (4) is a polymer chain composed of only α-olefins having 2 to 50 carbon atoms. More preferably, A of the vinyl group-containing compound is a polymer chain composed of only α-olefins having 2 to 20 carbon atoms.
More preferably, the vinyl group-containing compound A is an ethylene homopolymerized chain, a propylene homopolymerized chain, or an ethylene / α-olefin copolymer chain having 3 to 20 carbon atoms.

The vinyl group-containing compound represented by the above formula (4) has an ethylene-derived constituent unit in the range of 81 to 100 mol% and an α-olefin-derived constituent unit having 3 to 20 carbon atoms in the range of 0 to 19 mol%. It is preferably a certain ethylene / α-olefin copolymer. More preferably, it is an ethylene / α-olefin copolymer having an ethylene-derived structural unit in the range of 90 to 100 mol% and an α-olefin-derived structural unit having 3 to 20 carbon atoms in the range of 0 to 10 mol%. Is preferable. However, the total of the building blocks derived from ethylene and the building blocks derived from α-olefin having 3 to 20 carbon atoms is 100 mol%. In particular, it is preferable that the constituent unit derived from ethylene is 100 mol%.

Further, the vinyl group-containing compound represented by the above formula (4) has a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, Mw / Mn) measured by gel permeation chromatography (GPC) of 1.1 to Mn. It is preferably in the range of 3.0.

The vinyl group-containing compound represented by the above formula (4) preferably has a number average molecular weight (Mn) in the range of 100 or more and 500,000 or less, more preferably 100 or more and 100,000 or less, and more preferably 500 or more. More preferably 50,000 or less, and even more preferably 700 or more and 10,000 or less.

The vinyl group-containing compound represented by the above formula (4) preferably has a melting point of 70 ° C. or higher and 130 ° C. or lower.
More preferably, the vinyl group of the vinyl group-containing compound represented by the above formula (4) is preferably present at the end of the main chain, and more preferably the vinyl group is present only at the end of the main chain.

It is possible to confirm that the vinyl group is present at the end of the main chain by using ^{, for example, 13} CNMR and ^{1 1 HNMR.} For example, when A is an ethylene homopolymer, there is a method of confirming that tertiary carbon is not detected by ¹³ 1 HNMR and hydrogen of a vinyl group is detected by ^{1 1 HNMR. 1 Even in 1} HNMR alone, the structure can be confirmed by assigning the peak of each detected proton. For example, in the compound synthesized in Synthesis Example 1, the peak of chemical shift 0.81 ppm having a proton integral value of 3 is the methyl group at one end, and the peak of chemical shift 1.10-1.45 ppm is the main chain. The peak of the chemical shift 1.93 ppm with a methylene group and a proton integral value of 2 is 4.80, 4.86, 5.60-5.72 ppm with a methylene group adjacent to the terminal vinyl group and a proton integral value of 1, respectively. Is assigned to the terminal vinyl group, and there is no other peak of unknown attribution. Therefore, it can be confirmed that A is an ethylene homopolymer and has a structure containing a vinyl group only at the terminal. Alternatively, taking advantage of the fact that the vinyl group hydrogen present at the end of the main chain ^{has a shorter relaxation time in 1} HNMR measurement than the vinyl group hydrogen present in the side chain, for example, in the side chain. It is also possible to determine by a method of comparing the relaxation time with the hydrogen of the vinyl group of the polymer having a vinyl group.

In some cases, the chemical shift of the vinyl group in the side chain in ¹ HNMR can be determined by utilizing the fact that the magnetic field shift is lower than that of the vinyl group present at the terminal.
When the vinyl group-containing compound represented by the above formula (4) contains a vinyl group only at the end of the main chain, the terminal unsaturated rate (VE described later) calculated by ^{1 1 H-NMR is 60 mol.} It is preferably% or more and 100 mol% or less. One of the more preferable embodiments is ^{that the terminal unsaturated rate calculated by 1} H-NMR is 80 mol% or more and 99.5 mol% or less, and more preferably 90 mol% or more and 99 mol% or less.

The vinyl group-containing compound represented by the above formula (4) includes, for example, the transition metal compound (A) represented by the following formula (I), formula (II), or formula (III) and (B-1). A catalyst (B) consisting of at least one compound selected from an organometallic compound, (B-2) an organoaluminum oxy compound, and a compound that reacts with (B-3) a transition metal compound (A) to form an ion pair. ), It can be obtained by polymerizing or copolymerizing at least one or more olefins selected from olefins having 2 to 50 carbon atoms.

Transition metal compound represented by the formula (I)

（上記式（Ｉ）中、Ｍは周期律表４〜５族の遷移金属原子を示す。ｍは、１〜４の整数を示す。Ｒ⁵¹は、炭素数１〜５の直鎖炭化水素基（Ｃ_n'Ｈ_2n'+1，ｎ^'＝１〜５）または水素原子を示す。Ｒ⁵²〜Ｒ⁵⁶は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよい。また、ｍが２以上の場合にはＲ⁵²〜Ｒ⁵⁶で示される基のうち２個の基が連結されていてもよい。ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示す。ｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）
式（ＩＩ）で表される遷移金属化合物

(In the above formula (I), M represents a transition metal atom of Group 4 to 5 of the periodic table. M represents an integer of 1 to 4. R ⁵¹ is a linear hydrocarbon group having 1 to 5 carbon atoms. _{(C n 'H 2n' +} 1, n '= 1~5) or .R ⁵² to R ⁵⁶ represents a hydrogen atom may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, a hetero Indicates a cyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of them are mutually exclusive. They may be linked to form a ring. When m is 2 or more, ^{two of the groups represented by R 52 to} R ⁵⁶ may be linked. N is of M. It is a number satisfying the valence, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a hetero. Indicates a cyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and are indicated by X. A plurality of groups may be bonded to each other to form a ring.)
Transition metal compound represented by formula (II)

（上記式（ＩＩ）中、Ｍは周期律表第４〜５族の遷移金属原子を示す。ｍは、１〜４の整数を示す。Ｒ⁶¹は、１つまたは複数の置換基を有していてもよい３〜５員環の脂環式炭化水素基を示す。Ｒ⁶²〜Ｒ⁶⁶は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよい。また、ｍが２以上の場合にはＲ⁶²〜Ｒ⁶⁶で示される基のうち２個の基が連結されていてもよい。ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示す。ｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）。

(In the above formula (II), M represents a transition metal atom of Group 4 to 5 of the Periodic Table. M represents an integer of 1 to 4. R ⁶¹ has one or more substituents. Indicates a 3- to 5-membered alicyclic hydrocarbon group which may be present. R ^{62 to} R ⁶⁶ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocyclic compound residue. Indicates a group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these are linked to each other to form a ring. In addition, when m is 2 or more, ^{two of the groups represented by R 62 to} R ⁶⁶ may be linked. N satisfies the valence of M. A number, where X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic compound residue. Indicates a group, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be used. May combine with each other to form a ring.)

Transition metal compound represented by formula (III)

（上記式（ＩＩＩ）中、Ｍは周期律表第４〜５族の遷移金属原子を示す。ｍは、１〜４の整数を示す。Ｒ⁷¹は、１つまたは複数の置換基を有していてもよい炭素数４〜２０の少なくとも１つ以上の炭素を共有する２環性炭化水素基を示す。Ｒ⁷²〜Ｒ⁷⁶は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、これらのうちの２個以上が互いに連結して環を形成していてもよい。また、ｍが２以上の場合にはＲ⁷²〜Ｒ⁷⁶で示される基のうち２個の基が連結されていてもよい。ｎは、Ｍの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示す。ｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）。

(In the above formula (III), M represents a transition metal atom of Group 4 to 5 of the periodic table. M represents an integer of 1 to 4. R ⁷¹ has one or more substituents. .R ⁷² to R ⁷⁶ which indicates at least one or more bicyclic hydrocarbon group that shares the carbon of good 4-20 carbon atoms which may have may be the same or different from each other, a hydrogen atom, a halogen atom, Indicates a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Two or more groups may be connected to each other to form a ring, and when m is two or more, two groups among the groups ^{represented by R 72 to} R ^{76 may be connected.} n is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, Indicates a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. When n is 2 or more, the plurality of groups represented by X may be the same or different from each other. , Also, the plurality of groups represented by X may be bonded to each other to form a ring.)

Further, when A is composed of only ethylene-derived structural units and when A is composed of only propylene-derived structural units, it can also be produced by the following method.
(Polyolefin having ethylene homopolymerized chain)
(E1) The polyolefin polymerized chain having an ethylene homopolymerized chain can also be produced, for example, by the following method.

(A) A transition metal compound having a salicylaldoimine ligand as shown in JP-A-2000-2393132, JP-A-2001-2731 and JP-A-2003-73412 is used as a polymerization catalyst. Polymerization method.

(B) A polymerization method using a titanium-based catalyst composed of a titanium compound and an organoaluminum compound.
(C) A polymerization method using a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound.

(D) A polymerization method using a Ziegler-type catalyst composed of a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).
(Polyolefin having a propylene homopolymerized chain)
(E2) The polyolefin polymerized chain having the propylene homopolymerized chain can also be produced, for example, by the following method.

(A) A method for polymerizing propylene in the presence of a supported titanium-based catalyst such as a magnesium-supported titanium-based catalyst or a metallocene catalyst as shown in Japanese Patent Application Laid-Open No. 2004-262993.

(B) Compounds that form ionic complexes by reacting with transition metals in metal compounds as shown in JP-A-2000-191862, JP-A-2002-097325, etc., organoaluminum compounds, aluminoxane. A method of polymerizing propylene in the presence of a metallocene-based catalyst consisting of.

(Olefin / polyene copolymer)
An olefin / polyene copolymer (Z), which is one of the vinyl group-containing compounds according to the present invention, will be described.

Examples of the olefin include at least one selected from ethylene and an α-olefin having 3 to 12 carbon atoms.
Examples of α-olefins having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. Of these, preferably α-olefins having 3 to 10 carbon atoms, more preferably α-olefins having 3 to 8 carbon atoms, particularly preferably propylene, 1-butene, 1-hexene, 4-methyl-1- Penten is preferred.

Polyenes include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1, 3-Octadiene, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, etylidene norbornene, vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) ), Dicyclopentadiene, 2-methyl-1,4-hexadiene, 2-methyl-1,6-octadien, 7-methyl-1,6-octadien, 4-ethylidene-8-methyl-1,7-nonadien, 5,9-Dimethyl-1,4,8-decatorien and the like can be mentioned. Of these, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, butadiene, isoprene, 2-methyl-1,4-hexadiene or 2-methyl-1,6-octadien are preferred. Vinyl norbornene is particularly preferable because it has a bulky skeleton, which makes it possible to harden the wax even at a low density and is less likely to cause blocking of the wax product.

The olefin-polyene copolymer (Z) according to the present invention is a copolymer of ethylene and polyene, or at least one α-olefin and polyene selected from ethylene and an α-olefin having 3 to 12 carbon atoms. It is preferably a copolymer.

The olefin / polyene copolymer (Z) in the present embodiment contains 0.01 to 6.0 mol%, preferably 0.1 to 4.0 mol% of the constituent units derived from the polyene in 100 mol of all the constituent units. It is preferably contained in a ratio of%. When the olefin / polyene copolymer (Z) contains a structural unit derived from an α-olefin having 3 to 12 carbon atoms, the content thereof is 0.01 to 15 mol%, preferably 0.1. ~ 12 mol% is preferable.

When the olefin-polyene copolymer (Z) in the present embodiment contains a structural unit derived from the polyene in a proportion in the above range, the polymerization activity is also moderately high.
Further, when a structural unit derived from an α-olefin having 3 to 12 carbon atoms is contained in a proportion in the above range, a copolymer composition layer having less surface tackiness and excellent mechanical properties and impact resistance can be obtained. be able to.

(Z2) The olefin / polyene copolymer (Z) in the present embodiment has an average of 0.5 to 3.0 pieces / molecule, preferably 0.5 to 2.0 pieces / molecule, and more preferably 1.0 piece / molecule. It is preferable to have unsaturated groups in the range of ~ 2.0 elements / molecule, particularly preferably 1.0 to 1.9 elements / molecule, and particularly preferably 1.0 to 1.5 elements / molecule. When the unsaturated group content in the olefin / polyene copolymer (Z) is within the above range, the silicon-containing compound is added to most of the unsaturated groups in the olefin / polyene copolymer (Z). , The silylated polyolefin effectively acts on the filler (C), and a copolymer composition layer having excellent wear resistance can be obtained.

The unsaturated group content of the olefin / polyene copolymer (Z) is measured as follows. ^{By comparing the peak area of carbon in the unsaturated portion by 13} C-NMR with the peak area of total carbon, the number of unsaturated groups M per 1,000 carbons can be obtained. The unsaturated group content per molecule can be calculated by Mn × M / 14,000 using the number average molecular weight Mn.

In the present embodiment, the number of unsaturated groups M per 1,000 carbons is preferably 1.4 to 105, preferably 1.4 to 70, and more preferably 2.8 to 70.
(Z3) olefin-polyene copolymer in the present embodiment (Z) has a density measured by a density gradient tube method is 870 kg / m ³ or more, preferably 890 kg / m ³ or more, more preferably 910 kg / m ³ or more, Moreover, it is preferably 980 kg / m ³ or less, preferably 970 kg / m ³ or less, and more preferably 960 kg / m ³ or less. When the density of the olefin / polyene copolymer (Z) is within the above range, the tack feeling is small and the dispersibility in the copolymer composition layer is also excellent, so that the copolymer composition is excellent in abrasion resistance. A layer can be obtained.

(Z4) The olefin / polyene copolymer (Z) in the present embodiment has a melting point of 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably 90 ° C. or higher, as measured by a differential scanning calorimeter (DSC). It is preferably 100 ° C. or higher and 130 ° C. or lower, preferably 125 ° C. or lower, and more preferably 120 ° C. or lower. When the melting point of the olefin / polyene copolymer (Z) is within the above range, the tack feeling is small and the dispersibility in the copolymer composition layer is also excellent, so that the copolymer composition is excellent in abrasion resistance. A layer can be obtained.

(Z5) The olefin / polyene copolymer (Z) in the present embodiment has a number average molecular weight (Mn) of 400 to 5,000, preferably 400 to 4,000, as measured by gel permeation chromatography (GPC). It is more preferably in the range of 400 to 3,000, particularly preferably in the range of 1,500 to 2,500. When the Mn of the olefin / polyene copolymer (Z) is within the above range, the tack feeling is small and the dispersibility in the copolymer composition layer is also excellent, so that scratch resistance, durability and abrasion resistance are excellent. A copolymer composition layer having excellent properties and mechanical strength can be obtained.

(Z6) The olefin / polyene copolymer (Z) in the present embodiment has a ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight measured by GPC of 4.0 or less, preferably 3.5 or less. More preferably, it is 3.0 or less.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-equivalent values measured by gel permeation chromatography (GPC). Here, the measurement by GPC is performed under the conditions of temperature: 140 ° C. and solvent: orthodichlorobenzene.

(Z7) The olefin / polyene copolymer (Z) in the present embodiment has a needle insertion hardness of 15 dmm (1 dmm = 0.1 mm) or less, preferably 10 dmm or less, more preferably 3 dmm or less, and particularly preferably 1 d mm or less. Is preferable. The needle insertion hardness can be measured in accordance with JIS K2207. When the needle-insertion hardness of the olefin / polyene copolymer (Z) is within the above range, a copolymer composition layer having excellent wear resistance can be obtained.

The olefin / polyene copolymer (Z) in the present embodiment has the above (Z2) unsaturated group content, (Z3) density, (Z4) melting point, (Z5) number average molecular weight (Mn), and (Z6) Mw /. It is desirable to satisfy one or more of the conditions of Mn (Mw: weight average molecular weight) and (Z7) needle insertion hardness, more preferably two or more, and further preferably three or more. It is even more preferable to satisfy the above, particularly preferably to satisfy 5 or more, and particularly preferably to satisfy all 6. For example, in a particularly preferable embodiment, the (Z2-1) unsaturated group content is 0.5 to 3.0 elements / molecule, the (Z3-1) density is 870 to 980 kg / m ³ , and (Z4-1). ) Melting point is 70 to 130 ° C., (Z5-1) number average molecular weight (Mn) is 400 to 5,000, and (Z6-1) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less. In addition to these five, (Z7-1) needle-insertion hardness satisfying 15 dmm or less can be mentioned.

Further, the olefin / polyene copolymer (Z) according to the present embodiment is copolymerized using vinylnorbornene (5-vinylbicyclo [2.2.1] hept-2-ene) as a polyene. In some cases, the olefin / polyene copolymer (Z) has the above (Z2) unsaturated group content, (Z3) density, (Z4) melting point, (Z5) number average molecular weight (Mn), (Z6) Mw /. It is desirable to satisfy one or more of the conditions of Mn (Mw: weight average molecular weight) and (Z7) needle insertion hardness, more preferably two or more, and further preferably three or more. It is even more preferable to satisfy the above, particularly preferably to satisfy 5 or more, and particularly preferably to satisfy all 6. For example, in a particularly preferable embodiment, the (Z2-2) unsaturated group content is 0.5 to 2.0 elements / molecule, the (Z3-2) density is 890 to 980 kg / m ³ , and (Z4-2). ) Melting point is 80 to 130 ° C., (Z5-2) number average molecular weight (Mn) is 400 to 5,000, and (Z6-2) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less. In addition to these five, (Z7-2) needle-insertion hardness satisfying 15 dmm or less can be mentioned.

The olefin / polyene copolymer (Z) as described above is composed of, for example, a metallocene compound of a transition metal selected from Group 4 of the periodic table, an organic aluminum oxy compound and / or an ionized ionic compound, as described below. It can be produced using a system catalyst. Suitable metallocene catalysts in this embodiment include JP-A-2001-002731 or PCT applications already internationally published, WO / 2007/114102, WO / 2007/105483, WO / 2007/114009, WO / 2007. / 122906 and the like, for example, (A) metallocene compounds of transition metals selected from Group 4 of the periodic table, (B) (b-1) organoaluminum oxy compounds, (b-2) metallocene compounds (A). ) And at least one compound selected from (b-3) organoaluminum compounds, which are catalysts for olefin polymerization.

Specific examples of the metallocene compound of the transition metal selected from Group 4 of the (A) Periodic Table in the present embodiment include bis (cyclopentadienyl) zirconium monohydride, bis (cyclopentadienyl) zirconium dichloride, and bis. (1-Methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethyl ((t-butylamide) (tetramethyl-η ⁵⁾ -Cyclopentadienyl) silane) Titanium dichloride and the like.

Further, from the (B) (b-1) organoaluminum oxy compound, the compound (b-2) that reacts with the metallocene compound (A) to form an ion pair, and the (b-3) organoaluminum compound in the present embodiment. Specific examples of at least one selected compound include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and N, N-dimethylanilinium tetrakis (3). , 5-Ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenyl borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, trimethylaluminum, triisobutylaluminum and the like.

In the present embodiment, the case where the vinyl group-containing compound is represented by the above formula (4) is particularly preferable because it is excellent in abrasion resistance and durability and has less bleeding and blooming from the surface of the copolymer composition layer.

The silylated polyolefin (D) used in the present embodiment can be produced by any method, but is preferably obtained by sequentially carrying out the following [Step 1] and [Step 2]. Cyrilized polyolefin or a derivative thereof (D), or a mixture thereof.

[Step 1] A step of mixing and stirring a silicon-containing compound and a halogenated transition metal, and filtering the obtained suspension solution to obtain a transition metal catalyst composition (C) as a filtrate.
[Step 2] In the presence of the transition metal catalyst composition (C) obtained in the above [Step 1], the vinyl group-containing compound and the silicon-containing compound are reacted (however, two or more of the above-mentioned silicon-containing compounds per molecule. (Except when a compound having a SiH group is used and a compound having an average of 2.0 or more vinyl groups per molecule is used as the vinyl group-containing compound).

The method for producing the silylated polyolefin (D) according to the present invention will be described in detail below.
[Step 1]: Step of obtaining the transition metal catalyst composition (C) In [Step 1], the silicon-containing compound and the halogenated transition metal are mixed and stirred, and the obtained suspension solution is filtered to form a transition metal as a filtrate. Obtain the catalyst composition (C).

The halogenated transition metal is a halide of the transition metal of Group 3 to Group 12 of the Periodic Table of the Element Period, and is preferably a transition metal of Group 8 to Group 10 of the Periodic Table of the Element Period from the viewpoint of availability and economy. The halide is more preferably a halide of platinum, rhodium, iridium, ruthenium, osmium, nickel and palladium. More preferably, it is a halide of platinum. Further, it may be a mixture of two or more kinds of halogenated transition metals.
Examples of the halogen of the halogenated transition metal include fluorine, chlorine, bromine, and iodine, and among these, chlorine is preferable in terms of ease of handling.

Specific examples of the halogenated transition metal used in [Step 1] include platinum dichloride, platinum tetrachloride, platinum dibromide, platinum diiodide, ruthenium trichloride, rhodium tribromide, rhodium triiodide, and tri. Iridium chloride, iridium tetrachloride, iridium tribromide, iridium triiodide, ruthenium trichloride, ruthenium tribromide, ruthenium triiodide, osmium trichloride, osmium tribromide, osmium triiodide, nickel dichloride, di Examples thereof include nickel fluoride, nickel dibromide, nickel diiodide, palladium dichloride, palladium dibromide, and palladium diiodide. Of these, platinum dichloride, palladium dichloride, ruthenium trichloride, rhodium trichloride, and iridium trichloride are preferable, and platinum dichloride is most preferable.

The halogenated transition metal used in [Step 1] is usually a powdery solid, and the particle size is preferably 1000 μm or less, more preferably 500 μm or less. The larger the particle size, the longer the preparation time of the transition metal catalyst composition (C).

The amount of the silicon-containing compound and the halogenated transition metal used in [Step 1] is not particularly limited as long as the amount of the silicon-containing compound is 1 equivalent or more with respect to the halogenated transition metal, but is preferably 2 equivalents or more. If the amount of the silicon-containing compound is small, the stirring required for preparing the transition metal catalyst composition (C) becomes difficult.

Mixing and stirring of the silicon-containing compound and the halogenated transition metal in [Step 1] may be performed by any means as long as this is possible, but an appropriate amount of the halogenated transition metal is charged in a reaction vessel equipped with a stirrer under a nitrogen stream. , A silicon-containing compound is added thereto, and the mixture is stirred. In the case of a small amount, a stirrer tip may be placed in a sample tube, charged in the same manner, and stirred.

The mixing and stirring time of the silicon-containing compound and the halogenated transition metal is not particularly limited, but is usually 10 hours or more, preferably 20 hours or more, more preferably 60 hours or more, still more preferably 80 hours or more. Is. If the reaction time is short, the production ratio of the isomer vinylene derivative, which is an impurity in the silylated polyolefin obtained in the next [Step 2], increases, which is not preferable. There is no particular upper limit to the mixing and stirring time, but from an economical point of view, it is generally within one month.

The temperature of mixing and stirring the silicon-containing compound and the halogenated transition metal is not particularly limited as long as it is below the boiling point of the silicon-containing compound, but is usually in the range of 0 to 50 ° C, preferably in the range of 10 to 30 ° C. The pressure can usually be applied at normal pressure, but can also be applied under pressure or reduced pressure, if necessary.

In [Step 1], a solvent can be used if necessary. As the solvent to be used, one that is inert to the raw material silicon-containing compound and the halogenated transition metal can be used. Specific examples of solvents that can be used include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, and acetone. Examples thereof include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and methyl propyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, and halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, tetrachloroethane and perchloroethane. .. Of these, aromatic hydrocarbons such as toluene and xylene are particularly preferable.

When a solvent is used, the amount of the solvent used affects the solubility of the raw material, but is preferably 100 times by mass or less, more preferably 20 times by weight or less with respect to the raw material. In this embodiment, it is most preferable to carry out without solvent.

Next, the suspension solution obtained in the reaction is filtered to remove the solid content, and the transition metal catalyst composition (C) is obtained as a filtrate. The filtration method is not particularly limited, and general methods such as natural filtration, pressure filtration, and vacuum filtration can be used. The filter used for filtration is not particularly limited, and a cellulose filter paper, a glass fiber filter, a fluororesin or cellulose acetate membrane filter and the like can be appropriately used. Among these, it is preferable to use a fluororesin membrane filter from the viewpoints of uniformity of pore size, low hygroscopicity, chemical stability and the like. Further, as the filter used for filtration, it is preferable to use a filter having an eye size smaller than 10 μm, and it is more preferable to use a filter having an eye size of 1 μm or less. If a filter with a larger size is used, the solid content of the unreacted halogenated transition metal is mixed in the catalyst, and the catalyst becomes non-uniform, so that the amount of the vinylene derivative, which is an impurity of the synthetic object, is increased. It causes. It is also possible to wash the solid content using the above solvent during filtration.

The amount of solids removed by filtration, that is, the amount of unreacted halogenated transition metal, is usually 50% by weight or less, preferably 10% by weight or less, based on the amount of halogenated transition metal used. The reaction rate of the halogenated transition metal can be adjusted mainly by changing the preparation time.

The transition metal catalyst composition (C) thus prepared contains a nanocolloidal transition metal compound, a silicon-containing compound, and a solvent used as necessary. This transition metal catalyst composition (C) can be used as it is in the next [Step 2], but if necessary, the solvent is removed, concentrated, and diluted before being used in [Step 2]. You can also do it. Further, the silicon-containing compound can be further added and diluted to adjust the catalyst concentration.

Instead of carrying out [Step 1], a commercially available transition metal catalyst, for example, a platinum carrier (platinum black), a platinum chloride acid, a platinum-olefin complex, a platinum-alcohol complex, or a carrier of platinum such as alumina or silica is used. Examples thereof include those supported, but this may be used in [Step 2].

[Step 2]: In the step of reacting the vinyl group-containing compound with the silicon-containing compound [Step 2], in the transition metal catalyst composition (C) obtained in the above [Step 1], the vinyl group-containing compound and silicon React with the contained compound (however, the silicon-containing compound having two or more SiH groups in one molecule is used, and the vinyl group-containing compound has an average of 2.0 or more vinyl groups per molecule. (Except when using a compound) to obtain a silylated polyolefin.

Further, the silicon-containing compound used in [Step 2] may be different from the silicon-containing compound used in [Step 1], but preferably the same as the one used in [Step 1].

The amount ratio when the vinyl group-containing compound and the silicon-containing compound are reacted varies depending on the purpose, but the equivalent ratio of the vinyl group in the vinyl group-containing compound and the Si—H bond in the silicon-containing compound is 0.01 to 0.01. It is in the range of 10, preferably in the range of 0.1 to 2. Here, the amount of the silicon-containing compound is the total amount of the portion contained in the transition metal catalyst composition (C) used in [Step 1] and the portion newly added in [Step 2]. When the total amount of the silicon-containing compound required in [Step 1] is used, [Step 2] can be carried out without adding the silicon-containing compound.

The reaction between the vinyl group-containing compound and the silicon-containing compound is carried out in the presence of the transition metal catalyst composition (C) prepared in [Step 1]. ^{The amount ratio of the transition metal catalyst composition (C) to the vinyl group-containing compound is 10 -10} as the equivalent ratio of the vinyl group in the vinyl group-containing compound to the transition metal content in the transition metal catalyst composition (C). It is in the range of 10 to ^-1 , preferably in the range of 10 ^-7 to 10 ^-3 .

The reaction method in the reaction between the vinyl group-containing compound and the silicon-containing compound may be the final reaction, and the method is not limited, but is as follows, for example. The vinyl group-containing compound is charged into the reaction vessel, and the silicon-containing compound and the transition metal catalyst composition (C) are charged under a nitrogen atmosphere. The above reactor is set and stirred in an oil bath in which the internal temperature has been raised above the melting point of the vinyl group-containing compound in advance. After the reaction, the oil bath is removed and the mixture is cooled to room temperature, and the obtained reaction mixture is taken out into a poor solvent such as methanol or acetone and stirred for 2 hours. Then, the obtained solid is collected by filtration, washed with the above-mentioned poor solvent, and dried under a reduced pressure of 60 ° C. and 2 hPa or less to obtain the desired product.

The reaction between the vinyl group-containing compound and the silicon-containing compound in [Step 2] is preferably carried out in a reaction temperature range of 100 to 200 ° C., and more preferably at a temperature higher than the melting point of the vinyl group-containing compound to be reacted. .. If the reaction temperature is lower than 100 ° C., the reaction efficiency may decrease, which is not preferable. The pressure can usually be applied at normal pressure, but can also be applied under pressure or reduced pressure, if necessary.

In [Step 2], a solvent can be used if necessary. As the solvent to be used, one that is inert to the raw material silicon-containing compound and vinyl group-containing compound can be used. When the reaction is carried out under normal pressure, it is preferable to use a compound having a boiling point equal to or higher than the melting point of the vinyl group-containing compound to be reacted. Specific examples of solvents that can be used include aliphatic hydrocarbons such as n-hexane and decane, alicyclic hydrocarbons such as cyclohexane and cycloheptan, aromatic hydrocarbons such as toluene and xylene, ethyl acetate and acetic acid. Esters such as butyl, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, perchloroethane and the like. Examples include halogenated hydrocarbons. Of these, aromatic hydrocarbons such as toluene and xylene are particularly preferable.

When a solvent is used, the amount of the solvent used affects the solubility of the raw material, but is preferably 100 times by weight or less, more preferably 20 times by weight or less with respect to the raw material. In this embodiment, it is most preferable to carry out without solvent.

As described above, by reacting the vinyl group-containing compound with the silicon-containing compound in the presence of the transition metal catalyst composition (C), the silylated polyolefin (D) containing the structural unit represented by the above formula (1) is contained. ) Is obtained.

The reaction mixture containing the silylated polyolefin (D) after the reaction contains an unreacted vinyl group-containing compound and a vinylene derivative as a by-product, in addition to the silylated polyolefin (D). In some cases, unreacted silicon-containing compounds may be contained.

The proportion of the structure derived from the structural unit represented by the above formula (1) in the silylated polyolefin (D) according to the present invention is not particularly limited as long as the target function of the silylated polyolefin is expressed. It is usually 5 to 99% by weight, preferably 10 to 95% by weight. When the structural unit is within this range, the functions of scratch resistance, durability, abrasion resistance, and mechanical strength can be exhibited, and it is less likely to become oily and bleed out from the copolymer composition layer.

In the above method, since the highly active and highly selective transition metal catalyst composition obtained in [Step 1] is used, the reaction between the vinyl group-containing compound and the silicon-containing compound in [Step 2] is efficient. It progresses well. Therefore, the reaction rate of the double bond of the vinyl group-containing compound is usually 90% or more, preferably 95% or more, and the amount of the by-product vinylene derivative produced is higher than that of the silylated polyolefin (D). It is usually 10% by weight or less, preferably 5% by weight or less.

The silylated polyolefin (D) can be removed from the reaction mixture by reprecipitation to a poor solvent or sludge. The poor solvent may be any solvent as long as it has a low solubility of the silylated polyolefin, and can be appropriately selected, preferably one from which the above impurities can be removed. Specific examples of the poor solvent include acetone, methanol, ethanol, n-propanol, isopropanol, acetonitrile, ethyl acetate, n-hexane, n-heptane and the like, of which acetone and methanol are preferable.

The melt mass flow rate (MFR) of the obtained silylated polyolefin (D) measured at 190 ° C. and a load of 2.16 kg according to the method of JIS K7210 was 0.01 g / 10 minutes or more, preferably 0.1 g / 10 minutes. The above is more preferably 1.0 g / 10 minutes or more. There is no particular upper limit. This index is an index indicating that the silylated polyolefin (D) is not crosslinked to the extent that the fluidity of the copolymer composition is impaired.

Specific examples of the vinyl group-containing compound used in the present embodiment include the compound represented by the following formula (4) or the olefin / polyene copolymer (Z) as described above.

A-CH = CH ₂ ... (4)
(In the above formula (4), A is a polymerized chain containing one or more kinds of structural units derived from α-olefins having 2 to 50 carbon atoms.)
When the vinyl group-containing compound is a compound represented by the above formula (4), a structure (structure 4-1) in which A is composed of only α-olefins having 2 to 20 carbon atoms is preferable.

More preferably, the vinyl group-containing compound has _{a structure (structure 4-2) in which −CH = CH 2} is present at the end of the polymer main chain.
Even more preferably, the vinyl group-containing compound has _{a structure (structure 4-3) in which −CH = CH 2} exists only at the end of the polymer main chain.

Even more preferably, the vinyl group-containing compound has a structure (structure 4-4) (structure 4) in which A is composed of only α-olefin having 2 to 20 carbon atoms and -CH = CH ₂ is present at the end of the polymer main chain. It has a combination of -1 and structure 4-2).

Even more preferably, the vinyl group-containing compound has a structure (structure 4-5) in which A is composed of only α-olefin having 2 to 20 carbon atoms and −CH = CH ₂ is present only at the end of the polymer main chain (structure 4-5). It has a combination of structure 4-1 and structure 4-3).

When the vinyl group-containing compound is an olefin-polyene copolymer (Z), a structure using vinyl norbornene as the polyene is more preferable.
As described above, the silicon-containing compound of the present embodiment specifically has the structure of the above formula (2). Among them, preferable silicon-containing compounds in the case where the vinyl group-containing compound is represented by the above formula (4) and the case where the vinyl group-containing compound has the structure of the olefin / polyene copolymer (Z) are as follows.

When the vinyl group-containing compound is represented by the above formula (4), the silicon-containing compound preferably has a structure (structure 2-1) in which m = n = 1 in the above formula (2), and further, the above formula (structure 2-1). R ⁴¹ in Z in 2) is one selected from all hydrocarbon group and a halogen structures (structures 2-2) is more preferable (i.e. R ⁴¹ is preferably not a each is hydrogen atom.)

Further, when the vinyl group-containing compound is an olefin / polyene copolymer (Z), for example, when the number of vinyl groups in one molecule is 2.0 or more on average, the silicon-containing compound has the above formula. In (2), m = 1 and n = 0, and R ⁴¹ in Z in the above formula (2) has a structure (structure 2-3) in which all are selected from hydrocarbon groups and halogens, or the above. A compound having a structure (structure 2-4) in which m = 0, n = 0 in the formula (2) and ^{only one of R 41 in Z in the above formula (2) is a hydrogen atom is preferable.}

When the vinyl group-containing compound has an average of less than 2.0 vinyl groups in one molecule, the silicon-containing compound contains one SiH group such as the above structures 2-3 and 2-4. In addition to the compound having one in, it is also possible to use a compound having two or more Si—H bonds in one molecule, and for example, the above-mentioned structures 2-1 and 2-2 may be taken.

It is presumed that the silylated polyolefin and its derivative (D) have, for example, a structure represented by the formulas (5) to (9). Of course, the combination of the silicon-containing compound and the vinyl group-containing compound is not limited to these examples.

（上記各式中のｍ，ｎ，ｏ，ｐ，ｑは１以上の整数を表す。）

(M, n, o, p, q in each of the above equations represent integers of 1 or more.)

A particularly preferable embodiment and the reason for its estimation will be described below. Hereinafter, the portion derived from the vinyl group-containing compound may be referred to as a “polyolefin chain”, and the portion derived from a silicon-containing compound may be referred to as a “silicon-containing compound chain”. When the vinyl group-containing compound has a structure represented by the above formula (4), particularly the structure (4-5), and the silicon-containing compound has a structure (2-2), the silylated polyolefin (D) is (polyolefin). It is considered to have a structure like a block copolymer in which chains)-(silicon-containing compound chains)-(polyolefin chains) are bonded in this order. Specifically, a compound having an estimated structure as described in the above formula (5) can be exemplified.

When the vinyl group-containing compound has a structure (4-5) and the silicon-containing compound has a structure (2-1), and the silicon-containing compound has three or more SiH groups, the silylated polyolefin. In (D), in the block structure in which (polyolefin chain)-(silicon-containing compound chain)-(polyolefin chain) is bonded in this order, a structure in which the polyolefin chain is further bonded from the silicon-containing compound chain in a graft manner is formed. It is considered that it can be included.

When the vinyl group-containing compound has a structure (4-5) and the silicon-containing compound has a structure (2-3) and a structure (2-4), the silylated polyolefin (D) can be specifically illustrated. , It is considered that the structure is as shown in the above equations (6) and (8).

Further, the vinyl group-containing compound has a structure (4-5), and the silicon-containing compound has m = 0, n = 0, and Z in the formula (2) (−SiH (CH ₃ ) O−) ₆ −Si (CH). ₃ ) If it is ₂ O-Si (C ₆ H ₅ ) _2- , it may take the form of Eq. (7).

When the vinyl group-containing compound is an olefin / polyene copolymer (Z) and the silicon-containing compound has a structure (2-3), the silylated polyolefin (D) is a (polyolefin chain) and a (silicon-containing compound chain). ) Is grafted, and it is considered that the structure is as shown in the above formula (9).

A vinyl group that is presumed to have a block copolymer structure of (polyolefin chain)-(silicon-containing compound chain)-(polyolefin chain), for example, that is presumed to have the structure of the above formula (5). The silylated polyolefin obtained from the combination of the containing compound and the silicon-containing compound has a silylated polyolefin presumed to have a polyolefin chain as a graft chain from the silicon-containing compound chain, and the polyolefin chain has a silicon-containing compound chain as a graft chain. Then, it is considered that the molecular movement is easier than that of the silylated polyolefin. Therefore, for example, it is considered that the silylated polyolefin is more likely to collect on the surface of the molded product by high-temperature crosslinking using a mold. Further, in the case of the above structure, since the polyolefin chains are present at both ends of the silicon-containing compound chain, it is considered that bleed-out or bloom-out from the surface of the copolymer composition layer is unlikely to occur.
In addition to the above components, a cross-linking agent may be added to the copolymer composition according to the present invention.

<Crosslinking agent>
Examples of the cross-linking agent according to the present invention include vulcanizing agents such as sulfur and sulfur compounds, and organic peroxides. The cross-linking agent is not particularly limited as long as it exhibits the effects of the present invention, but is preferably 0.1 to 20 parts by weight, more preferably 0.3, based on 100 parts by weight of the copolymer (A). It is blended in a proportion of ~ 5 parts by weight.
In the present invention, vulcanizing agents such as sulfur and sulfur compounds are preferable because they have less odor than organic peroxides and therefore have excellent workability and can be processed satisfactorily.

《Vulcanizing agent》
Examples of the vulcanizing agent used in vulcanization as one of the cross-linking agents include sulfur and sulfur compounds. Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.

Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, and high molecular weight polysulfide. In addition, sulfur compounds that release active sulfur at the vulcanization temperature and vulcanize, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, and selenium dimethyldithiocarbamate, should also be used. Can be done. Of these, sulfur is preferably used. These sulfur and sulfur compounds are used alone or in combination of two or more.

The sulfur and the sulfur compound are not particularly limited as long as the effects of the present invention are exhibited, but are usually 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the copolymer (A). , More preferably 0.3 to 5 parts by weight, but it is desirable to appropriately determine the optimum amount according to the required physical properties. When sulfur or a sulfur compound is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator in combination.

<Vulcanization accelerator>
Specific examples of the sulfide accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazo-lusulfenamide, and N, N-diisopropyl-2-benzothiazolsulfenamide. Sulfenamide compounds such as 2-mercaptobenzothiazole, 2- (2', 4'-dinitrophenyl) mercaptobenzothiazole, 2- (4'-morpholinodithio) benzothiazole, di-2-dibenzothiazyldisulfide Thiazol compounds such as (MBTS); guanidine compounds such as diphenylguanidine, diorsotrilguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidinephthalate; acetaldehyde-aniline reactants, butylaldehyde-aniline condensates, hexa Aldamine or aldehyde-ammonia compounds such as methylenetetramine and acetaldehyde ammonia; imidazoline compounds such as 2-mercaptoimidazoline; thioyuria compounds such as thiocarbanilide, diethylthioureia, dibutylthioureia, trimethylthioyuria and diolsotrilthioyuria Thiuram compounds such as tetramethylthium monosulfide, tetramethylthium disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide; zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc di-n-butyl dithiocarbamate. (ZnBDC), zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate and other dithioate compounds; Examples include compounds such as (zinc oxide).

These vulcanization accelerators are not particularly limited as long as the effects of the present invention are exhibited, but are usually 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the copolymer (A). It is used in proportion to parts by weight, but it is desirable to appropriately determine the optimum amount according to the required physical properties.

《Organic peroxide》
The organic peroxide, which is one of the cross-linking agents, may be any one usually used for peroxide vulcanization such as rubber (copolymer composition). Specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t-butylcumyl peroxide, benzoyl. Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxyn) hexin-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 , 5-Mono (t-butylperoxy) -hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene and the like can be mentioned. Of these, dicumyl peroxide, di-t-butyl peroxide, and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides are used alone or in combination of two or more.

The organic peroxide is not particularly limited as long as it exerts the effect of the present invention, but is usually 0.0003 to 0.05 mol, preferably 0.001 to 0, based on 100 parts by weight of the copolymer (A). Although it is used in a ratio of 03 mol, it is desirable to appropriately determine the optimum amount according to the required physical properties.

When an organic peroxide is used as the cross-linking agent, it is preferable to use a cross-linking aid in combination. Specific examples of the cross-linking aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; and others. Maleimide-based compounds; divinylbenzene and the like can be mentioned. Such a cross-linking aid is used in an amount of 0.5 to 2 mol, preferably approximately equimolar, relative to 1 mol of the organic peroxide used.

(Other ingredients)
Depending on the performance, the copolymer composition according to the present invention may include various known additives generally used in the production of molded products, such as softeners, antistatic agents, processing aids, and alkoxysilanes. Compounds, activators, reaction inhibitors, colorants, dispersants, flame retardants, plasticizers, antioxidants, scorch inhibitors, UV absorbers, antistatic agents, lubricants, fungicides, kneading accelerators, tackifiers Agents, surfactants and the like may be appropriately selected and blended in an appropriate blending amount.

<Softener>
As the softening agent, a softening agent usually used for rubber (copolymer composition) or the like can be used.

Specifically, petroleum-based softeners such as process oils, lubricating oils, paraffins, liquid paraffins, petroleum asphalt, and vaseline; Fatty oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinolic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate; petroleum Examples thereof include synthetic polymer substances such as resin, atactic polypropylene, and Kumaron inden resin. Of these, petroleum-based softeners are preferably used, and process oils are particularly preferably used.

The amount of these softeners to be blended is not particularly limited as long as the effects of the present invention are exhibited, but is 150 parts by weight or less, preferably 130 parts by weight or less, based on 100 parts by weight of the copolymer (A).

<Anti-aging agent>
The use of anti-aging agents can further extend the life of the material. This is the same as in the case of ordinary rubber (copolymer composition) and the like.

Specific examples of the anti-aging agent used in the present invention include phenylnaphthylamine, 4,4'-(α, α-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine and the like. Aromatic secondary amine stabilizers; 2,6-di-t-butyl-4-methylphenol, tetrakis- [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) ) Propionate] Phenolic stabilizers such as methane; Thioether stabilizers such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfides; 2-Mercaptobenzoimidazole, etc. Benzoimidazole-based stabilizers; dithiocarbamate-based stabilizers such as nickel dibutyldithiocarbamate; quinoline-based stabilizers such as polymers of 2,2,4-trimethyl-1,2-dihydroquinolin. These anti-aging agents may be used alone or in combination of two or more.

Such an anti-aging agent is not particularly limited as long as it exerts the effect of the present invention, but is usually used in a ratio of 5 parts by weight or less, preferably 3 parts by weight or less with respect to 100 parts by weight (copolymer composition). However, it is desirable to appropriately determine the optimum amount according to the required physical property values.

<Processing aid>
As the processing aid, a compound used for processing such as ordinary rubber (copolymer composition) can be used. Specifically, higher fatty acids such as ricinolic acid, stearic acid, partiminic acid and lauric acid, higher fatty acid salts such as barium stearate, zinc stearate and calcium stearate, ricinolic acid ester, stearic acid ester, partimate ester and laurin. Examples thereof include higher fatty acid esters such as acid esters.

Such a processing aid is not particularly limited as long as it exerts the effect of the present invention, but is usually used in a ratio of 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the copolymer (A). However, it is desirable to appropriately determine the optimum amount according to the required physical property values.

<Surfactant>
As the surfactant, a compound used for ordinary rubber processing can be used.
Specifically, amines such as di-n-butylamine, dicyclohexylamine, monoeranolamine, triethanolamine, "Acting B (manufactured by Yoshitomi Pharmaceutical Co., Ltd.)," Acting SL (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), polyethylene glycol. , Diethylene glycol, polyethylene glycol, lecithin, trialilute meritate, zinc compounds of aliphatic and aromatic carboxylic acids (eg, "Structol activator 73", "Structol IB 531", "Structor FA541" Schill & Seilacher) (Manufactured by Nippon Zeon Co., Ltd.), octadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compound (eg, "Arcard 2HF" (manufactured by Lion Axo Co., Ltd.) and the like.

Such a surfactant is not particularly limited as long as it exerts the effect of the present invention, but is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass with respect to 100 parts by weight of the copolymer (A). It is about 0.5 to 4 parts by mass, more preferably about 0.5 to 4 parts by mass. The surfactant can be appropriately selected depending on the intended use, and can be used alone or in combination of two or more.

<Method for producing copolymer composition>
The copolymer composition according to the present invention includes the above-mentioned copolymer (A), the above-mentioned modified copolymer (B), the above-mentioned filler (C), and, if necessary, the above-mentioned silylated polyolefin (D). From various known additives generally used in the production of products such as rubber (copolymer composition) such as softeners, to general rubber (copolymer composition), as appropriate, together with the cross-linking agent and the like. Product) Can be prepared by the method for producing the compound.

As a method for producing a copolymer composition according to the present invention, for example, an internal mixer (sealed mixer) such as a Banbury mixer, a kneader, or an intermix is used to prepare the above components at a temperature of 80 to 170 ° C. Knead for 2-20 minutes. Then, if necessary, additives such as a cross-linking agent and a softening agent are added to the obtained mixture using rolls such as open rolls or a kneader, and if necessary, a vulcanization accelerator and a cross-linking aid are used. Can be prepared by additional mixing, kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensing.
Further, when the kneading temperature in the internal mixers is low, each of the above components can be kneaded at the same time together with a softener or the like.

<Molded product>
The molded product according to the present invention is a molded product having the above-mentioned copolymer composition, preferably the above-mentioned copolymer composition.

When the molded product according to the present invention is made of a vulcanized product, ion agglomerates are formed in the copolymer composition layer, so that the copolymer composition layer is highly rigid and excellent. It has both mechanical properties (stretchability) and rubber elasticity. Therefore, it is particularly preferable because the copolymer composition layer can be thinned to have desired physical properties (particularly, abrasion resistance and durability).

The copolymer composition layer is not particularly limited as long as the effects of the present invention are exhibited, but the durometer A hardness measured according to JIS K6253 is preferably 10 to 100. If the durometer A hardness is less than 10, the rubber layer is too soft and the wear resistance may decrease. Further, when the durometer A hardness exceeds 100, for example, when the molded product is used for the surface layer of the paddy roll, the rice may be damaged during paddying and the occurrence rate of so-called crushed rice may increase.

The durometer A hardness is more preferably 40 to 100, and further preferably 60 to 100 from the viewpoint of the balance between the fracture rate and wear resistance of rice.
The durometer A hardness of the copolymer composition layer is preferably about 40 to 90 when the rice to be padded is relatively soft japonica rice or the like, and the rice to be padded is relatively hard indica rice or the like. In the case of, it is preferably about 60 to 100.

The "copolymer composition layer" in the present invention corresponds to the "rubber portion" referred to in JIS K 9124.
The copolymer composition layer preferably has a tan δ peak temperature (Tg) of 10 ° C. or lower. This is because it exhibits appropriate rubber elasticity at the temperature of the copolymer composition layer at the time of use, which is 30 to 50 ° C.

The DIN wear amount of the copolymer composition layer is preferably 10 to 500 mg. If the DIN wear amount is less than 10 mg, the rate of occurrence of crushed rice may increase during paddling, and if it exceeds 500 mg, the durability becomes insufficient. The amount of DIN wear can be measured according to the DIN wear test of JIS-K6264-2: 2005.

When the copolymer composition layer is used on the surface of the paddy roll, the thickness of the copolymer composition layer is not particularly limited as long as the effect of the present invention is obtained. It can be appropriately set according to the specifications and the JIS standard (JIS B 9214). Here, the thickness of the copolymer composition layer means a value of 1/2 of the difference between the outer diameter and the inner diameter of the copolymer composition layer when not in use.

[Manufacturing method of molded product]
As a method for producing a paddy roll as a molded product according to the present invention, for example, the copolymer composition is injection-molded into a mold in which a core material portion of a rice roll is preset and crosslinked. To.

Further, in the copolymer composition layer, an uncrosslinked composition is once prepared by the method as described above in the same manner as when a general copolymer composition is crosslinked, and then this compounded copolymer is prepared. It can also be obtained by forming the composition into an intended shape and then cross-linking the composition. Vulcanization is preferable as the cross-linking.

The uncrosslinked composition prepared as described above can be molded and crosslinked by various molding methods such as an extrusion molding machine, a calendar roll or a press, but may be used for compression molding, injection molding, injection molding and the like. By molding, the characteristics can be most exhibited when molding and cross-linking.

That is, in the case of compression molding, the uncrosslinked copolymer composition weighed in advance is placed in a mold, and after the mold is closed, it is heated at a temperature of 120 to 270 ° C. for 30 seconds to 120 minutes to achieve the desired crosslinking. The above-mentioned copolymer composition layer is obtained.

In the case of injection molding, a ribbon-shaped or pellet-shaped copolymer composition is supplied to the pot in a preset amount by a screw. Subsequently, the preheated copolymer composition is fed into the mold by a plunger in 1 to 20 seconds. The desired copolymer composition layer is obtained by heating the copolymer composition at a temperature of 120 to 270 ° C. for 30 seconds to 120 minutes after injecting the copolymer composition.

In the case of injection molding, a pre-weighed copolymer composition is placed in a pot and injected into a mold by a piston in 1 to 20 seconds. By injecting the copolymer composition and then heating at a temperature of 120 to 270 ° C. for 30 seconds to 120 minutes, the desired crosslinked copolymer composition layer can be obtained.

[Paddy roll]
The paddy roll of the present invention has the copolymer composition layer on the surface of the core material portion. Usually, the paddy roll is obtained by baking a copolymer composition layer on the surface of the core material and then polishing or finishing the surface. As the core material portion, for example, a core material portion used in a conventionally known paddy roll such as a metal metal fitting drum can be used. Examples of the material of the core material include aluminum, stainless steel, iron, molybdenum, and titanium. Further, the shape and size of the core material portion are not particularly limited, and as with the conventional product, it is appropriate according to the specifications of the paddy shaving machine to which the paddy shaving roll is attached and the JIS standard (JIS B 9214: copolymer composition roll for shaving). Can be set.

In the paddy roll of the present invention, a primer layer and / or an adhesive layer may be formed between the core material portion and the copolymer composition layer in order to further improve the adhesion between the two. Further, the outer peripheral surface of the core material portion may be subjected to a surface treatment for enhancing the adhesion with the copolymer composition layer. The formation of the adhesive layer is not particularly limited as long as the effects of the present invention are exhibited, but for example, a phenolic adhesive or the like can be used. The formation of the primer layer is not particularly limited as long as the effect of the present invention is obtained, but for example, it is carried out by using a urethane-based, polyester-based, silane-based, polyamide-based, phenol-based primer, a silane coupling agent, or the like. Can be done. Examples of the surface treatment include the formation of a roughened surface, and the roughened surface may be formed by, for example, a blasting treatment, a grinding treatment, an etching treatment, a plating treatment, a polishing treatment, an oxidation treatment, or the like.

It is preferable that the roundness of the cross section (cross section perpendicular to the rotation axis at the time of use) of the paddy roll is 0.5 mm or less. If the roundness exceeds 0.5 mm, the spacing between the paddy rolls will vary greatly during use, which may reduce the removal rate or increase the rate of crushed rice.

Further, according to the present invention, an agricultural threshing machine provided with the paddy roll can be preferably obtained.
[Manufacturing method of paddy roll]
The paddy roll can be produced, for example, by going through the following steps (1) and (2).

(1) First, the core material part is prepared. The core material portion can be produced by a conventionally known method, for example, by aluminum die casting or the like. Then, if necessary, an adhesive layer and / or a primer layer is formed on the outer peripheral surface of the core material portion. Further, if necessary, the outer peripheral surface of the core material portion is surface-treated.

(2) Next, a copolymer composition layer is formed around the core material portion. As a forming method, for example, the core material portion is placed in a cylindrical mold, and then the copolymer composition is injected into the gap between the outer peripheral surface of the core material portion and the inner wall surface of the mold to determine a predetermined value. A copolymer composition layer can be formed by cross-linking under the conditions. The conditions can be referred to above.

The crosslinking conditions are not particularly limited as long as the effects of the present invention are exhibited, and can be appropriately set, but usually, conditions of heating at 100 to 160 ° C. for 30 to 90 minutes can be adopted. Further, after carrying out the cross-linking treatment and removing the mold from the mold, post-cross-linking may be carried out under the conditions of, for example, 100 to 160 ° C. for 3 to 48 hours.

Since the copolymer composition according to the present invention has significantly improved dispersibility of the filler and suitable moldability, the composition can be suitably laminated on the surface of the core material portion. Therefore, according to the present invention, a copolymer composition layer having a uniform density over the entire surface of the core material portion, having excellent wear resistance and durability, and being able to be used for a long period of time is formed. The paddy roll can be suitably manufactured.
In the method for producing a paddy roll, the surface of the copolymer composition layer may be formed by grinding, if necessary. It is not necessary to perform grinding while the mold is removed from the mold.

[How to use paddy roll]
The paddy roll of the present invention is used by attaching two paddy rolls as a set to a conventionally known copolymer composition roll type paddy machine (for example, an agricultural threshing machine).

The pair of paddy rolls are usually attached to the paddy shaving machine in parallel so as to have a predetermined interval, and each of the paddy rolls is rotated in opposite directions and at different rotation speeds. Then, when rice husks are thrown between the rice husk rolls in this state, the rice husks are removed from the rice husks due to the difference in peripheral speed between the rice husk rolls.

The distance between the paddy roll gaps and the rotation speed (peripheral speed) of each paddy roll are not particularly limited, and depend on various conditions such as the specifications of the paddy roll, the type of paddy rice to be put in, the drying rate, the processing speed, and the removal rate. It may be set appropriately.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
(Measurement and calculation method)
The molecular weight, melting point (Tm), yield, conversion rate, isomerization rate, and melt mass flow rate (MFR) of the silylated polyolefin were measured and calculated by the methods described below.

[M1] Method for Measuring Molecular Weight The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using GPC-150 manufactured by Millipore as follows. That is, the separation column was TSK GNH HT, and the column size used was 7.5 mm in diameter and 300 mm in length. The column temperature was 140 ° C., orthodichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.025% by mass of BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant were used for the mobile phase, and the mixture was moved at 1.0 ml / min. .. The sample concentration was 0.1% by mass, and the sample injection amount was 500 microliters. A differential refractometer was used as the detector. A calibration curve was prepared using standard polystyrene and converted to a polyethylene-equivalent value according to a conventional method.
In the following synthesis example, the number of moles of the raw material polymer is represented by a value based on (Mn).

[M2] Method for measuring melting point As the melting point (Tm), the peak top temperature obtained by measuring with DSC was adopted. The device used was a DSC-60A manufactured by Shimadzu Corporation. Alumina was used as the control cell, and the nitrogen flow rate was set to 50 ml / min. Further, the measurement was carried out at 10 ° C./min under a heating condition of 30 ° C. to 300 ° C. Before this temperature rise measurement, the temperature of the resin is once raised to about 200 ° C., held for 5 minutes, and then lowered to room temperature (25 ° C.) at 20 ° C./min to unify the thermal history of the resin. Is preferable.

[M3] Measurement / calculation method of yield, conversion rate, isomerization rate, and terminal unsaturated rate by NMR analysis The yield, conversion rate, isomerization rate, and terminal unsaturated rate of silylated polyolefin ^{are determined by 1 1} H-NMR. Will be done. The yield is the ratio of the number of moles of the obtained silylated polyolefin to the number of moles of the raw material vinyl group-containing compound, and the conversion rate is the ratio of the same number of moles consumed to the number of moles of the raw material vinyl group-containing compound, the isomerization rate. Is the ratio of the number of moles of vinylene produced to the number of moles of the raw material vinyl group-containing compound, and the terminal unsaturated rate is the main chain of the raw material vinyl group-containing compound with respect to the total number of terminal vinyl groups and terminal methyl groups. Defined as the proportion of terminal vinyl groups. The terminal unsaturated rate and the number of vinyl groups per 1,000 carbons are generally applied to the vinyl group-containing compound which is the raw material, but when hydrosilylation is insufficient, it is an index of the residual amount of the unreacted raw material. It may also be applied to silylated polyolefins.

For example, the peak (C) of 6 protons of the ethoxy group methylene of the silylated polyolefin obtained by hydrosilylating a main chain terminal vinyl group-containing compound consisting of ethylene only with triethoxysilane is 3.8 ppm, and the isomerized vinylene group. The peak (D) for 2 protons is observed at 5.4 ppm. When hydrosilylation is insufficient, the peak (E) for 2 protons of the unreacted vinyl group is observed at 4.8 to 5.1 ppm, and the peak (F) for 1 proton is observed at 5.6 to 5.8 ppm. To. Regarding the raw material vinyl group-containing compound, the main chain methylene (G) for 2 protons was observed at 1.0 to 1.5 ppm, and the compound having no vinyl group at the end of the main chain was the terminal methyl (H) for 3 protons. ) Is observed at 0.8 ppm. Furthermore, a peak (I) for two protons on the carbon adjacent to the double bond is observed at 1.9 ppm.

If the peak areas of the peaks (C), (D), (E), (F), (G), (H) and (I) are SC, SD, SE, SF, SG, SH and SI, respectively. , Yield (YLD (%)), conversion rate (CVS (%)), isomerization rate (ISO (%)), terminal unsaturated rate (VE (%)) are calculated by the following formulas.
YLD (%) = (SC / 3) / (SC / 3 + SD + SE) x 100
CVS (%) = {1-SE / (SC / 3 + SD + SE)} x 100
ISO (%) = SD / (SC / 3 + SD + SE) x 100
VE (%) = SE / (SE / 2 + SH / 3) x 100

[M4] Method for measuring melt mass flow rate (MFR) The melt mass flow rate (MFR) of polyethylene as a vinyl group-containing compound is measured at 190 ° C. and a load of 2.16 kg using a melt indexer T-111 manufactured by Tokyo Seiki Co., Ltd. did.

In the examples and comparative examples, the following copolymers and the like were used.
(1) Ethylene / α-olefin / non-conjugated polyene copolymer (A)
As an ethylene / α-olefin / non-conjugated polyene copolymer (A), Mitsui Elastomer (registered trademark) K-9720 manufactured by Mitsui Chemicals Co., Ltd. (constituent unit derived from ethylene: 77% by weight, derived from diene) Structural unit: 10.4 wt%, Mooney viscosity ML _{(1 + 4)} (100 ° C.) (ASTM D 1646): 20) was used.

(2) Cyrilized polyolefin (β)
[Synthesis Example 1]
(Synthesis of polyethylene having a vinyl group at one end)
3.89 g (15.0 mmol) of 3-cumyl-5-methylsalitylaldehyde, 30 ml of toluene and 2.54 g of ethylamine (40% aqueous solution, 22.5 mmol) were charged in a 100 ml reactor that had been sufficiently dried and replaced with nitrogen. The mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography to obtain a yellow oily compound (L-1).

1.12 g (4.00 mmol) of the compound (L-1) obtained above and 25 ml of diethyl ether were charged in a 100 ml reactor sufficiently dried and substituted with argon, cooled to −78 ° C., and stirred. 2.58 ml of n-butyllithium (n-hexane solution, 1.55 M, 4.00 mmol) was added dropwise to this over 5 minutes, and the mixture was stirred at the same temperature for 2 hours, then slowly warmed to room temperature to room temperature. The lithium salt was prepared by stirring for another 3 hours. This solution was added dropwise to 25 ml of a tetrahydrofuran solution containing 0.76 g (2.00 mol) of _{the ZrCl 4} (THF) ₂ complex cooled to −78 ° C. After completion of the dropping, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 12 hours, the solvent was distilled off from the reaction solution. The obtained solid was dissolved in 50 ml of methylene chloride, and the insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, the precipitated solid was reprecipitated with n-hexane, and dried under reduced pressure to give a yellow powder compound (B-1).

1000 ml of heptane was charged at room temperature into a stainless steel autoclave having an internal volume of 2000 ml sufficiently substituted with nitrogen, and the temperature was raised to 150 ° C. Subsequently, the inside of the autoclave ^{was pressurized to 30 kg / cm 2} G with ethylene to maintain the temperature. Press-fit 0.5 ml (0.5 mmol) of a hexane solution (1.00 mmol / ml in terms of aluminum atom) of MMAO (manufactured by Toso Finechem), and then 0.5 ml of a toluene solution (0.0002 mmol / ml) of compound B-1. (0.0001 mmol) was press-fitted to initiate polymerization. After polymerizing at 150 ° C. for 30 minutes in an ethylene gas atmosphere, the polymerization was stopped by press-fitting a small amount of methanol. The resulting polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours.

^{By 1 1} H-NMR measurement, it was clarified that the obtained polymer was homopolyethylene and contained a double bond only at one end. The physical characteristics of this single-ended double bond-containing ethylene-based polymer (P-1) (elemental substance) were as follows.
Melting point (Tm) 123 ° C
Mw = 4770, Mw / Mn = 2.25 (GPC)
End unsaturated rate 97%

[Synthesis Example 2]
(Preparation of Platinum Catalyst Composition (C-1))
In a 50 ml sample tube containing a magnetic stirrer chip, 0.50 g of platinum (II) chloride was added to hydrosilane A (HS (A), manufactured by Momentive Performance Materials Japan GK, product number: XF40-C2195) having the following structure. It was suspended in (10 ml) and stirred at room temperature under a nitrogen stream. After stirring for 190 hours, about 0.4 ml of the reaction solution was collected with a syringe, filtered using a 0.45 μm PTFE filter, and the filtrate was collected in a 10 ml sample tube. A platinum catalyst having a platinum concentration of 3.8% by mass. The composition (C-1) was obtained.
Hydrosilane A (HS (A)): HSi (CH 3) 2 O - (- Si (CH 3) 2 -O-) 18 -Si (CH 3) 2 H

[Synthesis Example 3]
(Introduction of polyethylene having a terminal vinyl group into hydrosilane-1)
25.1 g (11.8 mmol) of the one-terminal vinyl group-containing ethylene-based polymer (P-1) obtained in [Synthesis Example 1] was charged into a 300 ml two-necked flask, and hydrosilane A (11.8 mmol) was charged under a nitrogen atmosphere. 8.7 g (5.9 mmol; equivalent to 11.8 mmol as a Si—H group) of HS (A) and the platinum catalyst composition (C-1) prepared in [Synthesis Example 2] are combined with hydrosilane A (HS (A)). ^{), 150 μl (1.4 × 10 -6} mmol in terms of Pt) of (C-1a) diluted 200 times was charged. The above reactor was set in an oil bath whose internal temperature had been raised to 130 ° C. in advance, and the mixture was stirred. After about 3 minutes the polymer melted. Then, after 6 hours, the mixture was cooled, about 200 ml of methanol was added, the contents were taken out into a 300 ml beaker, and the mixture was stirred for 2 hours. Then, the solid was collected by filtration, washed with methanol, and dried at 60 ° C. under a reduced pressure of 2 hPa or less to obtain 33.1 g of a silylated polyolefin (A-1) as a white solid. As a result of NMR analysis, the obtained silylated polyolefin (A-1) had a yield of 98%, an olefin conversion rate of 100%, and an isomerization rate of 2%. The MFR was equal to or higher than the upper limit of measurement (MFR> 100 g / 10 min), and the polyorganosiloxane content in (A-1) calculated from the molecular formula was 26% by mass.

(3) Filler (C)
As the filler (C), Silica VN3 GRTtype (primary particle size: 15 nm, particle size of secondary aggregate: 18 μm, specific surface area: 200 m ² / g) manufactured by Toso Silica Co., Ltd. was used.

In the present invention, each physical property was evaluated as follows.
(1) Hardness test The flat parts of the vulcanized molded article were overlapped to make 12 mm, and the hardness (durometer A hardness) was measured according to JIS K6253.

(2) Tensile test A tensile test was performed on the vulcanized molded product in accordance with JIS K 251 under the conditions of a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min. M50), modulus at 100% stretch (M100), modulus at 200% stretch (M200), modulus at 300% stretch (M300), strength at break (TB) and elongation at break (EB) were measured.

(3) DIN friction test (DIN wear amount)
Using the vulcanized molded body, a disk-shaped test piece having a diameter of 16.0 ± 0.2 mm and a thickness of 6 mm or more was prepared in accordance with JIS-K6264-2: 2005, and the test piece was subjected to DIN wear. Using a testing machine, a drum with a diameter of 150.0 ± 0.2 mm and a length of 500 mm is rotated at 40 times / minute, and the amount of wear when the load is 1 kgf and the wear distance is 40.0 ± 0.2 m ( DIN wear amount: unit mg) was measured.

(4) Crosslink Density A sheet-shaped sample was cut into a size of 20 mm × 20 mm × 2 mmt, and then immersed in toluene for 37 ° C. × 72 hours to swell according to JIS K 6258 (1993), and the Flory-Rehner formula (B) The effective network chain density (crosslink density) was calculated.

式（Ｂ）中、ν（個／ｃｍ³）は有効網目鎖密度（架橋密度）であり、純ゴム１ｃｍ³中の有効網目鎖の数であり、Ｖ_Rは膨潤した架橋ゴム中の純ゴムの容積分率であり、Ｖ₀は溶剤の分子容であり、μはゴム−溶剤間の相互作用定数＝０．４９であり、Ａはアボガドロ数である。

In formula (B), ν (pieces / cm ³ ) is the effective mesh chain density (crosslink density), which is the number of effective mesh chains in ^{1 cm 3 of} _{pure rubber, and V R} is the pure rubber in the swollen crosslinked rubber. V ₀ is the molecular volume of the solvent, μ is the rubber-solvent interaction constant = 0.49, and A is the Avogadro number.

(5) Pain effect (filler dispersion index)
A sample was punched out from the vulcanized molded product to prepare a test piece. For this sample, the strain rate dependence of the storage elastic modulus G'was measured using a dynamic viscoelasticity tester. The measurement conditions are as follows.
Dynamic viscoelasticity tester (RDS): Rheometrics Sample: Used by punching a 2 mm sheet into a circle with a diameter of 25 mm.
Temperature: 100 ° C
Distortion rate: 0.01% to 10%
Frequency: 10Hz

Filler dispersion with the obtained storage elastic modulus G'at a strain rate of 0.01% as G'(0.01%) and the storage elastic modulus G'at a strain rate of 1.00% as G'(1.00%). The sex index FDI (%) was calculated from the following equation (1).
FDI = G'(1.00%) / G'(0.01%) x 100 ... (1)

[Comparative Example 1]
Using MIXTRON BB MIXER (manufactured by Kobe Steel Co., Ltd., BB-4 type, volume 2.95 L, rotor 4 WH), 50 parts by mass of silica (C) is coupled to 100 parts by mass of K-9720. 1 part by mass of silicon (Si69, manufactured by Evonik) as an agent, 1 part by mass of polyethylene glycol (PEG # 4000, manufactured by Sanyo Kasei Kogyo Co., Ltd.) as a surfactant, zinc oxide (zinc oxide) as a vulcanization accelerator , # 1, manufactured by Huxuitec) by 5 parts by mass, stearic acid as a processing aid by 1 part by mass, and process oil (Diana Process Oil PS-430, manufactured by Idemitsu Kosan Co., Ltd.) as a softener by kneading 15 parts by mass. , The composition before vulcanization was obtained. The kneading conditions were a rotor rotation speed of 50 rpm, a floating weight pressure of 3 kg / cm ² , a kneading time of 5 minutes, and a kneading discharge temperature of 145 ° C.

Next, after confirming that the temperature of the formulation reached 40 ° C., a 6-inch roll was used to add di-2-benzothiazolyl disulfide (MBTS, Ouchi Shinko Kagaku Kogyo) as a vulcanization accelerator to the formulation. 0.5 parts by mass of N-cyclohexyl-2-benzothiazolesulfenamide (CBS, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) as a vulcanization accelerator, 0.5 parts by mass of a vulcanization accelerator Tetramethylsulfur disulfide (TMTD, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) is 1.0 part by mass, and zinc dibutyldithiocarbamate (ZnBDC, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) is 1.0 as a vulcanization accelerator. Sulfur was kneaded by mass and 1.0 parts by mass as a vulcanizing agent. The kneading conditions are that the roll temperature is front roll / rear roll = 50 ° C./50 ° C., the roll rotation speed is front roll / rear roll = 18 rpm / 15 rpm, the roll gap is 5 mm, and the kneading time is 8 minutes. A copolymer composition (combination) was obtained.

Next, this compound was vulcanized at 180 ° C. for 15 minutes using a press molding machine to prepare a rubber sheet (vulcanized molded product) having a thickness of 2 mm.
The obtained vulcanized molded product was subjected to a hardness test, a tensile test, a DIN friction test, a crosslink density, and a filler dispersion index by the above method. The results are shown in Table 1.

[Example 1]
In addition to the formulation used in Comparative Example 1, the copolymer (A): as a graft-modified ethylene / α-olefin copolymer (B) grafted with an unsaturated carboxylic acid or a derivative thereof with respect to 100 parts by mass. Maleic anhydride-modified ethylene / 1-butene copolymer (Toughmer (registered trademark) МD715, manufactured by Mitsui Elastomers Singapore Pte Ltd, MFR (190 ° C., 2.16 kg): 1.5 g / 10 min, density: 872 kg / m ³ , The same procedure as in Comparative Example 1 was carried out except that a copolymer composition in which 5 parts by weight was added (melting point: 40 to 80 ° C.) measured by differential scanning calorimetry (DSC) was used. The results are shown in Table 1.

[Example 2]
In addition to the formulation used in Comparative Example 1, the copolymer (A): 100 parts by mass, 5 parts by mass of the silylated polyolefin (β), and the maleic anhydride-modified ethylene / 1-butene copolymer (1-butene copolymer). Toughmer (registered trademark) МD715, manufactured by Mitsui Elastomers Singapore Pte Ltd, MFR (190 ° C., 2.16 kg): 1.5 g / 10 min, density: 872 kg / m ³ , melting point measured by differential scanning calorimetry (DSC): The same procedure as in Comparative Example 1 was carried out except that a copolymer composition in which 5 parts by mass was added (40 to 80 ° C.) was used. The results are shown in Table 1.

As shown in Table 1, a copolymer composition (Comparative Example 1) containing no graft-modified ethylene / α-olefin copolymer (B) grafted with an unsaturated carboxylic acid or a derivative thereof according to the present invention is available. A copolymer composition containing a graft-modified ethylene / α-olefin copolymer (B) grafted with an unsaturated carboxylic acid or a derivative thereof according to the present invention, while the amount of wear is 84 mmg (Example 1, Example 1). In Example 2), the amount of wear is as small as 68 mmg and 60 mmg, and it is clear that the wear resistance is excellent.

Claims (2)

It is a paddy roll having a copolymer composition layer on the surface, and the copolymer composition layer is
Ethylene, α-olefin with 4 to 20 carbon atoms, non-conjugated polyene copolymer (A), 100 parts by mass,
A graft-modified ethylene / α-olefin copolymer (B) grafted with an unsaturated carboxylic acid or a derivative thereof (B) 0.1 to 10 parts by mass, and a filler (C) satisfying the following requirement (C-1) (however, carbon A paddy roll comprising a copolymer composition containing 1 to 100 parts by mass (excluding black).
(C-1) The average particle size is 10 μm to 50 μm. The paddy roll according to claim 1, wherein the α-olefin of the ethylene / α-olefin / non-conjugated polyene copolymer (A) having 4 to 20 carbon atoms is 1-butene.