JP2017155159A - Husking roll and manufacturing method of the husking roll - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a husking roll improving dispersibility of a filler to a rubber, especially silica, excellent in abrasion resistance and further in durability, capable of being used over long time and having a rubber layer on a surface.SOLUTION: A husking roll is a husking roll having a rubber layer on a surface, the rubber layer is a composition containing 100 pts.wt. of a rubber component (α), total 0.01 to 100 pts.wt. of silylated polyolefin and/or a derivative hereof (β) which is a reaction product of a silicon-containing compound containing a constitutional unit represented by the following formula (1) and a vinyl group-containing compound having number average molecular weight (Mn) measured by a gel permeation chromatography (GPC) of 100 to 500,000, excluding silylated polyolefin and a derivative thereof which is a reaction product of a silicon-containing compound having 2 or more SiH groups in a molecule as the silicon-containing compound and a vinyl group-containing compound having average 2.0 or more vinyl groups in a molecule as the vinyl group-containing compound and 1 to 100 pts.wt. of a filler (C) satisfying the following requirement (C-1), excluding carbon black.SELECTED DRAWING: None

Description

  The present invention relates to a hulling roll and a method for producing the hulling roll.

  An agricultural threshing machine in which a hulling roll having a rubber layer is attached to the surface of a core part is used for threshing rice or the like (for example, Patent Document 1). As the rubber, nitrile rubber (NBR), styrene butadiene rubber (SBR) or the like is used (for example, Patent Document 2).

  However, since rubber is easily worn and deteriorated by use, various studies have been made on a rubber layer that has superior wear resistance and durability and can be used for a long period of time and a hulling roll having the rubber layer ( For example, Non-Patent Document 1 and Patent Document 1).

  Usually, various kinds of reinforcing materials are appropriately blended to improve the wear resistance of rubber, but carbon black is considered to have the highest effect of improving wear resistance. However, considering the use of rice threshing, the use of carbon black, which can be a black foreign substance, is not preferred, and the market demands a hulling roll with excellent wear resistance without the addition of carbon black. Yes.

  Moreover, the hardened | cured material of the thermoplastic urethane rubber composition is also used as a rubber layer (patent document 3). However, the layer made of the cured product has a problem in that it has poor durability and is easily deteriorated by hydrolysis with moisture.

JP 2001-29809 A Japanese Patent Laid-Open No. 04-203518 Japanese Patent Laying-Open No. 2015-202480

Journal of the Japan Rubber Association, Wear of Rubber Rolls for Firth, Ichiro Imase, Vol. 44, No. 2 (1971), pages 187-194

  As an alternative to rubbers containing carbon black, rubbers containing other fillers, particularly rubbers containing silica, have been studied because they are relatively excellent in wear resistance. However, since silica is inferior in dispersibility in rubber, silica-blended rubber has poor moldability, and the rubber cannot provide a hull roll having sufficient wear resistance.

  The present invention seeks to solve the problems associated with the prior art as described above, and improves the dispersibility of fillers, particularly silica, for rubber, has excellent wear resistance, and also has excellent durability, An object of the present invention is to provide a hulling roll having a rubber layer on its surface that can be used for a long time.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a rubber component and a specific silylated polyolefin and / or a derivative thereof (however, represented by the following formula (1) and one molecule) And a silicon-containing compound having two or more SiH groups, a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is from 100 to 500,000, and an average of 2.0 per molecule By blending a silylated polyolefin, which is a reaction product with a vinyl group-containing compound having at least one vinyl group, and derivatives thereof, together with a filler (but excluding carbon black), the dispersibility of the filler can be improved, Thereby, since the moldability is improved, a rubber layer excellent in wear resistance and durability can be suitably obtained, and the rubber layer is removed from the hulling roll. Found that can be used across the hulling roll which is excellent in wear resistance and durability by using the surface for long-term, and have completed the present invention.

The hulling roll of the present invention is
A hulling roll having a rubber layer on the surface,
The rubber layer has a rubber component (α),
A silicon-containing compound containing a structural unit represented by the following formula (1) and a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) are 100 to 500 with respect to 100 parts by weight of the rubber component. Silylated polyolefin and / or a derivative thereof (β) which is a reaction product with a vinyl group-containing compound of 1,000,000 (however, the silicon-containing compound having two or more SiH groups per molecule as the silicon-containing compound, and 0.01 to 100 parts by weight in total of a silylated polyolefin, which is a reaction product with a vinyl group-containing compound having an average of 2.0 or more vinyl groups per molecule as a vinyl group-containing compound, and derivatives thereof ,
It is characterized by comprising a composition containing 1 to 100 parts by weight of filler (C) (excluding carbon black) satisfying the following requirement (C-1) with respect to 100 parts by weight of the rubber component.

-Si (R ¹ ) H-Y ^1- (1)
(In the 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).

  (C-1) The average particle size is 10 μm to 50 μm.

The rubber component (α) is an ethylene / α-olefin / nonconjugated polyene copolymer (A) satisfying the following requirements (A-1) and (A-2): 0 to 99 parts by weight, -1) and (B-2) containing 1 to 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer (B) (provided that the copolymer (A) and the copolymer (B ) Is 100 parts by weight)
It is preferable.

  (A-1) The structural unit derived from ethylene (E) is contained at 40 to 70% by weight.

(A-2) Mooney viscosity ML _{(1 + 4)} (100 ° C.) at 100 ° C. obtained by measurement according to ASTM D 1646 is 1-50.

  (B-1) A structural unit derived from ethylene (E) is contained in an amount exceeding 70% by weight and 99% by weight or less.

(B-2) Mooney viscosity ML _{(1 + 4)} (100 ° C.) at 100 ° C. obtained by measurement according to ASTM D 1646 is ₁ to 90.

  It is preferable that the composition further contains a crosslinking agent (D).

  The crosslinking agent (D) is a vulcanizing agent, and the vulcanizing agent is preferably contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the rubber component.

  It is preferable that the durometer A hardness measured according to JIS K6253 of the rubber layer is 10 to 100.

The method of manufacturing the hulling roll is
It is a method for producing a hulling roll having a rubber layer on the surface,
The manufacturing method comprises:
100 parts by weight of rubber component (α),
A silicon-containing compound containing a structural unit represented by the following formula (1) and a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) are 100 to 500 with respect to 100 parts by weight of the rubber component. Silylated polyolefin and / or a derivative thereof (β) which is a reaction product with a vinyl group-containing compound of 1,000,000 (however, the silicon-containing compound having two or more SiH groups per molecule as the silicon-containing compound, and 0.01 to 100 parts by weight in total of a silylated polyolefin, which is a reaction product with a vinyl group-containing compound having an average of 2.0 or more vinyl groups per molecule as a vinyl group-containing compound, and derivatives thereof ,
A composition containing 1 to 100 parts by weight of filler (C) (excluding carbon black) satisfying the following requirement (C-1) with respect to 100 parts by weight of the rubber component is used as the crosslinking agent (D). It includes a step of crosslinking in the presence to obtain a rubber layer.

-Si (R ¹ ) H-Y ^1- (1)
(In the 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).

  (C-1) The average particle size is 10 μm to 50 μm.

  According to the present invention, by blending a rubber component and a specific silylated polyolefin and / or a derivative thereof together with a filler, the dispersibility of the filler can be improved, and the wear resistance and durability are extremely excellent. A hulling roll having a rubber layer on the surface that can be used can be provided.

[Coffin roll]
Hereinafter, the hulling roll having a rubber layer on the surface of the present invention and the method for producing the hulling roll will be specifically described.

[Rubber layer]
The hulling roll of the present invention has a rubber layer on the surface of the core part. The rubber layer is composed of a composition containing a rubber component (α), a specific silylated polyolefin and / or a derivative thereof (β), and a specific filler (C) in specific amounts. The rubber layer is preferably made of a crosslinked product obtained by crosslinking the composition in the presence of a crosslinking agent (D).

(Rubber component (α))
The rubber component (α) according to the present invention is not particularly limited as long as it exhibits rubber elasticity and exhibits the effects of the present invention, and examples thereof include raw rubbers such as natural rubber (NR) and synthetic rubber. Synthetic rubbers include, for example, olefin copolymer rubbers (for example, ethylene / α-olefin / non-conjugated polyene random copolymers such as ethylene-propylene rubber and ethylene / propylene / diene copolymer rubber (EPDM)), Diene rubbers such as nitrile rubber (NBR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR), chlorinated butyl rubber (CIIR) and brominated butyl rubber (BIIR), etc. These water additives such as halogenated butyl rubber, isoprene rubber (IR), acrylic rubber (ACM), polyisobutylene, and hydrogenated styrenic thermoplastic elastomer (SEBS) can be mentioned. The rubber component may be used alone or in combination of two or more.

  Among these, from the viewpoint of dispersibility with respect to silylated polyolefin and / or its derivative (β) and filler (C), particularly silica, natural rubber, EPDM and other ethylene / α-olefin / non-conjugated polyene random copolymer Preferably, the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the ethylene / α-olefin / non-conjugated polyene copolymer (B) described below are more preferable, the copolymer (A) and the copolymer More preferably, the copolymer (B) is contained in a specific amount.

  Further, when the olefin copolymer rubber and other rubber are used in combination as the rubber component (α), the other rubber is used in a total amount of 100 parts by weight of the olefin copolymer rubber and the other rubber. On the other hand, it is not limited as long as the effect of the present invention is exhibited, but it is preferably 40 parts by weight or less, more preferably 5 to 20 parts by weight.

(Ethylene / α-olefin / non-conjugated polyene copolymer (A))
The ethylene / α-olefin / non-conjugated polyene copolymer (A) according to the present invention is a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms. And a copolymer rubber that includes a structural unit derived from a non-conjugated polyene and satisfies the following requirements (A-1) and (A-2). The copolymer (A) preferably satisfies the following requirements (A-1) to (A-3).

  The copolymer (A) 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 include propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1 Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyldecene-1, 11-methyldodecene-1, 12-ethyltetradecene-1, etc. Is mentioned. Among these, α-olefins having 3 to 10 carbon atoms are preferable, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are more preferable, and propylene is particularly preferable.

  These α-olefins are 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 Chain unconjugated such as 1,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene and 4-ethylidene-1,7-undecadiene Diene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2 Cyclic non-conjugated dienes such as -norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene and norbornadiene; 2,3-diisopropylidene-5-norbornene 2-ethylidene-3-isopro Isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. trienes and 4-ethylidene-8-methyl-1,7-nonadiene and the like. Of these, a mixture of 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene is preferable, and 5-ethylidene-2 More preferred are mixtures of -norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

  These non-conjugated polyenes are used alone or in combination of two or more.

・ Requirement (A-1)
The copolymer (A) contains a constituent unit derived from ethylene (E) in an amount of usually 40 to 70% by weight, preferably 43 to 65% by weight, more preferably 45 to 55% by weight, and an α-olefin (O ) -Containing structural units usually in an amount of 30 to 60% by weight, preferably 35 to 57% by weight, more preferably 45 to 55% by weight (provided that structural units derived from ethylene (E) and α-olefin (O ) Is defined as 100% by weight). The structural unit derived from the non-conjugated polyene (P) is usually 1.0 to 20.0% by weight based on 100% by weight of the structural unit derived from the ethylene (E) and the structural unit derived from the α-olefin (O). %, Preferably 3.0 to 15.0% by weight, more preferably 4.0% to 14.0% by weight. It is preferable for it to be in the above range since both physical properties and production efficiency can be achieved.

The composition of the copolymer (A) can be measured using, for example, ¹³ C-NMR in accordance with ASTM D 3900 and ASTM D 6047.

・ Requirements (A-2)
The copolymer (A) has a Mooney viscosity ML _{(1 + 4)} (100 ° C.) at 100 ° C. of 1 to 50, more preferably 10 to 50, obtained by measurement according to ASTM D 1646. More preferably, it is in the range of more than 30 and 50 or less. It is preferable that the Mooney viscosity is in the above range because good processability is exhibited.

・ Requirement (A-3)
The copolymer (A) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 1.0 to 5.0 dl / g, preferably 1.0 to 4.0 dl / g.

  Specific examples of the copolymer (A) include ethylene / propylene / 5-ethylidene-2-norbornene random copolymers, ethylene / propylene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene random copolymers. A polymer etc. can be illustrated.

(Ethylene / α-olefin / non-conjugated polyene copolymer (B))
The ethylene / α-olefin / non-conjugated polyene copolymer (B) according to the present invention is a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms. And a copolymer rubber that includes a structural unit derived from a non-conjugated polyene and satisfies the following requirements (B-1) and (B-2). The copolymer (B) preferably satisfies the following requirements (B-1) to (B-3).

  This copolymer (B) may be used individually by 1 type, and may be used in combination of 2 or more types. The copolymer (B) is not limited to structural isomers such as trans isomers and cis isomers as long as the effects of the present invention are exhibited.

  Examples of the α-olefin include those exemplified for the copolymer (A). α-olefins may be used alone or in combination of two or more. Among these, α-olefins having 3 to 10 carbon atoms are preferable, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are more preferable, and propylene is particularly preferable.

  Examples of the non-conjugated polyene include those exemplified for the copolymer (A). You may use a nonconjugated polyene individually or in combination of 2 or more types. Of these, a mixture of 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene is preferable, and 5-ethylidene-2 More preferred are mixtures of -norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.

・ Requirement (B-1)
The copolymer (B) contains a structural unit derived from ethylene (E) in an amount of usually more than 70% by weight and 99% by weight or less, preferably 70 to 90% by weight, more preferably 70 to 85% by weight. The structural unit derived from α-olefin (O) is usually 1 wt% or more and less than 30 wt%, preferably 10 to 30 wt%, more preferably 15 to 30 wt% (however, derived from ethylene (E) And the structural unit derived from the α-olefin (O) is 100% by weight). The structural unit derived from the non-conjugated polyene (P) is usually 1.0 to 20.0% by weight based on 100% by weight of the structural unit derived from the ethylene (E) and the structural unit derived from the α-olefin (O). %, Preferably 3.0 to 15.0% by weight, more preferably 4.0 to 14.0% by weight. It is preferable for it to be in the above range since both physical properties and production efficiency can be achieved.

The composition of the copolymer (B) can be measured using, for example, ¹³ C-NMR based on ASTM D 3900 and ASTM D 6047.

・ Requirements (B-2)
The copolymer (B) has a Mooney viscosity ML _{(1 + 4)} (100 ° C.) at 100 ° C. of usually 1 to 90, more preferably 1 to 60, which is obtained by measurement according to ASTM D 1646. More preferably, it is in the range of 1-30. When the Mooney viscosity is in the above range, it is preferable because good processability and good physical properties are exhibited.

・ Requirements (B-3)
The copolymer (B) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 1.0 to 5.0 dl / g, preferably 1.0 to 4.0 dl / g.

  Specific examples of the copolymer (B) include ethylene / propylene / 5-ethylidene-2-norbornene random copolymer, ethylene / propylene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene random copolymer. A polymer etc. can be illustrated.

(Production method of copolymer (A) and copolymer (B))
The copolymer (A) and the copolymer (B) can be produced using a known polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It does not specifically limit as a polymerization method, It can carry out by liquid phase polymerization methods, such as solution polymerization, suspension polymerization, a bulk polymerization method, a gas phase polymerization method, and other well-known polymerization methods. In addition, 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, Espren (registered trademark) manufactured by Sumitomo Chemical Co., Ltd., and Mitsui EPT (registered trademark) manufactured by Mitsui Chemicals, Inc.

(Silylated polyolefin and its derivatives (β))
The silylated polyolefin according to the present invention has a silicon-containing compound containing a structural unit represented by the following formula (1) and a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 100 to 500, It is a reaction product with a vinyl group-containing compound that is 000 or less (however, the silicon-containing compound having two or more SiH groups per molecule is used, and the vinyl group-containing compound has an average of 2. Compounds having 0 or more vinyl groups, that is, silicon-containing compounds having 2 or more SiH groups per molecule as the silicon-containing compounds, and an average of 2.0 or more vinyls per molecule as the vinyl-containing compounds Except when using silylated polyolefin, which is a reaction product with a vinyl group-containing compound having a group, or a derivative thereof).

-Si (R ¹ ) H-Y ^1- (1)
The formula (1), R ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group, Y ¹ is O, S or NR ³⁰ (R ³⁰ is a hydrogen atom or a hydrocarbon group).

Although the structure of silylated polyolefin is not certain, for example, —Si—H in a silicon-containing compound containing the structural unit of the above formula (1) and —CH═CH ₂ (vinyl group) in a vinyl group-containing compound. It is thought that it may contain a -Si-C-C- structure which is produced by the reaction. However, when a compound having two or more SiH groups per 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, The silylated polyolefin is considered to have a high possibility of having a network structure, for example, and this case is excluded in this embodiment.

  A rubber layer comprising a composition comprising a rubber component (α), the silylated polyolefin and / or derivative thereof (β), and a filler (C), preferably the composition in the presence of a crosslinking agent (D) The present inventors speculate that a rubber layer made of a cross-linked product obtained by cross-linking has improved surface silicon concentration, suppressed surface free energy of the rubber layer, and good wear resistance.

  In addition, the silylated polyolefin has a better uneven distribution of the silylated polyolefin in the rubber layer compared to conventional additives such as silicone additives and metal soaps, which prevents the filler (β) from falling off. In addition, the silylated polyolefin has a high affinity with silica because it can form a hydrophobic bond with the filler (β), in particular with the rubber layer, and with hydrogen in SiH and silica. The present inventors infer that the hulling roll having such a rubber layer on the surface has good wear resistance and durability because bleeding or blooming on the surface is difficult to occur.

  The silicon-containing compound according to the present invention is a hydrosilane compound having a structural unit represented by the following formula (1).

-Si (R ¹ ) H-Y ^1- (1)
The formula (1), R ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group, 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 a hydrocarbon group, a C2-C40 hydrocarbon group is preferable and a C2-C20 hydrocarbon group is more preferable. Specific examples 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, and octadecyl group. A linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a norbornyl group; and 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, and a cyclohexenyl group.

  Examples of the aryl group include phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group and the like.

  In addition, the above hydrocarbon group may contain one or more heteroatoms. Specific examples include groups in which at least one hydrogen of these groups is substituted with a group containing a halogen atom, oxygen, nitrogen, silicon, phosphorus, or sulfur.

  In one embodiment, the silicon-containing compound has a structure represented by 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 each independently a hydrogen atom, a halogen atom or a hydrocarbon group,
R ²² and R ²⁴ are each independently a halogen atom or a hydrocarbon group,
Y ²¹ and Y ²² are each independently O, S or NR ³⁰ (R ³⁰ is a hydrogen atom or a hydrocarbon group);
m is 0 or 1,
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, 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 a hydrocarbon group);
l is an integer of 0 to 10,000.

However, in the above formula (2), when m = n = 0, in the above formula (3), at least one R ⁴¹ is a hydrogen atom.

  In addition, the definition of the halogen atom and hydrocarbon group in the said Formula (2) and the said Formula (3) is the same as the definition in the said Formula (1).

  It is also a typical embodiment that the hydrocarbon groups in the above formulas (1), (2), and (3) are composed of only carbon atoms and hydrogen atoms.

  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 still more preferably 50 or less silicon atoms. By using the silylated polyolefin using such a silicon-containing compound, the silylated polyolefin is well-distributed in the rubber layer and can prevent the filler (β) from falling off. Due to the high affinity, bleeding or blooming on the surface of the rubber layer is unlikely to occur, so that a rubber layer having excellent scratch resistance and durability can be obtained. The scratch resistance referred to here includes wear resistance, friction resistance, and slidability.

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

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

  In one embodiment, in the above formula (2), m = 1 and n = 0, that is, a silicon-containing compound having 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.

Another particularly preferable silicon-containing compound is a compound in which m = 1 and n = 0 in the above formulas (2) and (3), 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 the present embodiment are shown below. Examples of the silicon-containing compound of this embodiment include a compound having one SiH group.

  Examples of the silicon-containing compound having one SiH group include, for example, a compound represented by the following formula (2a), in which a part or all of the methyl groups in the formula (2a) are ethyl, propyl, phenyl, 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 a compound include, but are not limited to, the following compounds.

_{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 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 block-like or disordered. It may be.

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

_{Si (CH 3) 3 O-} SiH (CH 3) -O-Si (CH 3) 3
Examples of the silicon-containing compound of this embodiment include compounds having two or more SiH groups.

  Examples of the silicon-containing compound having two or more SiH groups include, for example, methyl hydrogen polysiloxane represented by the following formula (2c), a part or all of the methyl groups in the following formula (2c) being ethyl groups, propyl And a compound 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) Or the compound etc. which were substituted by the hydrocarbon group which may contain one or more hetero atoms, such as an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, etc. are 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 sum of g and h is, for example, 1000, preferably 300, and more preferably 50. ).

In the above formula (2d), the order in which the —Si (CH ₃ ) ₂ —O— units and the —SiH (CH ₃ ) —O— units are arranged is not particularly limited. Or statistically random.

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

  As another example of the silicon-containing compound having two or more SiH groups, for example, methyl hydrogen polysiloxane represented by the following formula (2e), a part or all of the methyl groups in the following formula (2e) is ethyl And a compound 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 following compounds.

_{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 another example of the silicon-containing compound having two or more SiH groups, for example, methyl hydrogen polysiloxane represented by the following formula (2f), a part or all of the methyl groups in the following formula (2f) is ethyl And a compound 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).

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

HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) _k — (— SiH (CH ₃ ) —O—) ₁ —Si (CH ₃ ) ₂ H (2 g)
(In the above formula (2g), k and l are each an integer of 1 or more, and the upper limit of the sum of k and l is, for example, 1000, preferably 300, and more preferably 50).

Further, the order in which the —Si (CH ₃ ) ₂ —O— units and the —SiH (CH ₃ ) —O— units are arranged is not particularly limited, and is statistically random regardless of whether they are block-like or disordered. It may be.

  The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the vinyl group-containing compound according to the present invention is usually 100 or more and 500,000 or less, and more preferably 100 or more and 100,000 or less. . When the number average molecular weight is not less than the above lower limit value, the resulting silylated polyolefin can be further suppressed from bleeding or blooming from the rubber layer. When the amount is not more than the above upper limit, dispersibility of the silylated polyolefin in the rubber layer is improved, and handling of the rubber 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 conversion values.

  The vinyl group-containing compound will be described below.

  The vinyl group-containing compound is usually obtained by polymerizing or copolymerizing one or more olefins 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-heptene, 3,4-dimethyl-1-heptene, 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 and trans-2-butene; 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-heptene, 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-octene, 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-methylvinylidenecyclopentane A vinylidene compound such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc .; -Arylvinylidene compounds such as methylstyrene, α-ethylstyrene, 2-methyl-3-phenylpropylene; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, methacrylate Functional group-substituted vinylidene compounds such as phosphoric acid-n-butyl, isobutyl methacrylate, tert-butyl methacrylate, 2-cyanopropylene, 2-aminopropylene, 2-hydroxymethylpropylene, 2-fluoropropylene, 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, cycloheptene, cyclooctene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 5,6-dihydrodicyclopentadiene, 3a, 4,5,6,7,7a-hexahydro-1Hindene , Tricyclo 6.2.1.0 ^{2, 7]} undec-4-ene, cyclopentadiene, aliphatic cyclic olefins containing internal double bonds, such as dicyclopentadiene; cyclopent-2-enyl benzene, cyclopent-3-enyl benzene, Contains aromatic rings such as cyclohex-2-enylbenzene, cyclohex-3-enylbenzene, indene, 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, 1,4-methino 1,4,4a, 9a tetrahydrofluorene 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-octadiene, 1,4-octadiene, 1, 5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, Examples thereof include cyclic polyenes having two or more double bonds and chain polyenes having two or more double bonds, such as 5,9-dimethyl-1,4,8-decatriene.

  Moreover, the C2-C50 olefin 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] hept-5-ene-2,3-dicarboxylic acid, and sodium, potassium, lithium and zinc salts thereof Unsaturated carboxylic acid metal salts such as magnesium salt and calcium salt; Unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride and bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride Acid anhydride; methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, acrylic acid-2-ethylhexyl, etc. Unsaturated carboxylic acid ester; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate , Vinyl esters such as vinyl stearate and vinyl trifluoroacetate; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate and monoglycidyl itaconate; halogenated such as vinyl chloride, vinyl fluoride and allyl fluoride Olefin; Unsaturated cyano compound such as acrylonitrile and 2-cyano-bicyclo [2.2.1] hept-5-ene; Unsaturated ether compound such as methyl vinyl ether and ethyl vinyl ether; Acrylamide, methacrylamide, N, N-dimethyl Unsaturated amides such as acrylamide; methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, etc. Group-containing styrene derivatives; N- vinylpyrrolidone and the like.

  In a preferred embodiment, the vinyl group-containing compound is a compound having a structure represented by the following formula (4) and having a number average molecular weight of 100 or more and 500,000 or less.

A-CH = CH ₂ (4)
Here, in said formula (4), A is a polymeric chain containing the structural unit derived from 1 or more types of C2-C50 alpha olefin.

  In the above formula (4), preferably, part A of the vinyl group-containing compound is a copolymer of two or more 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 polymer 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 an α-olefin having 2 to 50 carbon atoms. More preferably, A of the vinyl group-containing compound is a polymer chain composed of only an α-olefin having 2 to 20 carbon atoms. More preferably, A of the vinyl group-containing compound is an ethylene homopolymer chain, a propylene homopolymer chain, or an ethylene / C3-C20 α-olefin copolymer chain.

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

  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 1.1. 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 500 or more. 50,000 or less is further preferable, and 700 or more and 10,000 or less is even more preferable.

  Moreover, it is preferable that melting | fusing point of the vinyl group containing compound represented by the said Formula (4) is 70 to 130 degreeC.

  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.

In addition, it can confirm that a vinyl group exists in the terminal of a principal chain, for example using ¹³ CNMR and ¹ HNMR. For example, when A is an ethylene homopolymer, there is a method in which tertiary carbon is not detected by ¹³ CNMR and vinyl group hydrogen is detected by ¹ HNMR. ^{Even in 1} HNMR alone, the structure can be confirmed by assigning each detected proton peak. 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 a methyl group at one end, and the peak of chemical shift 1.10-1.45 ppm is the main chain. The peak of 1.93 ppm chemical shift with methylene group and proton integral value of 2 is 4.80, 4.86, 5.60-5.72 ppm with methylene group adjacent to the terminal vinyl group and proton integral value of 1, respectively. Is attributed to the terminal vinyl group and no other unidentified peak exists, so that it can be confirmed that A is an ethylene homopolymer and has a structure containing a vinyl group only at the terminal. As another method, by utilizing the fact that the hydrogen of the vinyl group present at the end of the main chain is shorter in the ¹ H NMR measurement than the hydrogen of the vinyl group present in the side chain, It can also be determined by a method of comparing the relaxation time with hydrogen of the vinyl group of the polymer having a vinyl group.

In some cases, the chemical shift in ¹ HNMR of the vinyl group in the side chain can be determined using the fact that the magnetic field shifts lower than 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 terminal of the main chain, the terminal unsaturation rate (VE described later) calculated by ¹ H-NMR is 60 mol. % Or more and 100 mol% or less is preferable. One of the more preferable embodiments is one in which the terminal unsaturation calculated by ¹ H-NMR is 80 mol% or more and 99.5 mol% or less, more preferably 90 mol% or more and 99 mol% or less.

  The vinyl group-containing compound represented by the above formula (4) is, for example, a transition metal compound (A) represented by the following formula (I), formula (II), or formula (III), and (B-1) A catalyst comprising at least one compound selected from an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with a transition metal compound (A) to form an ion pair (B ) To polymerize or copolymerize at least one olefin selected from olefins having 2 to 50 carbon atoms.

  Transition metal compound represented by formula (I)

(In the above formula (I), M represents a transition metal atom of groups 4 to 5 in the periodic table. M represents an integer of 1 to 4. R ⁵¹ represents a linear hydrocarbon group having 1 to 5 carbon atoms. (C _{n ′} H _{2n ′ + 1} , n ^′ = 1 to 5) or a hydrogen atom, R ^{52 to} R ⁵⁶ may be the same as or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, hetero A cyclic 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; It may be linked to form a ring, and when m is 2 or more, two of the groups represented by R ^{52 to} R ⁵⁶ may be linked. And X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron An element-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. A plurality of groups may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)
Transition metal compound represented by formula (II)

(In the above formula (II), M represents a transition metal atom of Groups 4 to 5 of the periodic table. M represents an integer of 1 to 4. R ⁶¹ has one or more substituents. R ^{62 to} R ⁶⁶ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue. Group, 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 these are linked together 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, and n satisfies the valence of M. X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, An element-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. A plurality of groups may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring).

  Transition metal compound represented by formula (III)

(In the above formula (III), M represents a transition metal atom of Groups 4 to 5 of the periodic table. M represents an integer of 1 to 4. R ⁷¹ has one or more substituents. And a bicyclic hydrocarbon group that shares at least one or more carbon atoms having 4 to 20 carbon atoms, and R ^{72 to} R ⁷⁶ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, Indicates a hydrocarbon group, heterocyclic 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, Two or more may be connected to each other to form a ring, and when m is 2 or more, two groups out of 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 element-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group is shown. When n is 2 or more, a 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 bonded to each other to form a ring).

  Moreover, when A consists only of the structural unit derived from ethylene, and when it consists only of the structural unit derived from propylene, it can also be produced by the following method.

(Polyolefin having ethylene homopolymer chain)
(E1) A polyolefin polymer chain having an ethylene homopolymer chain can also be produced, for example, by the following method.

  (A) A transition metal compound having a salicylaldoimine ligand as shown in JP 2000-239312 A, JP 2001-27331 A, JP 2003-73412 A, etc. is used as a polymerization catalyst. Polymerization method.

  (B) A polymerization method using a titanium-based catalyst comprising a titanium compound and an organoaluminum compound.

  (C) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.

  (D) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane).

(Polyolefin having propylene homopolymer chain)
(E2) A polyolefin polymer chain having a propylene homopolymer chain can also be produced, for example, by the following method.

  (A) A method of polymerizing propylene in the presence of a supported titanium-based catalyst such as a magnesium-supported titanium-based catalyst or a metallocene catalyst as disclosed in JP-A-2004-262993.

  (B) Compounds that form an ionic complex by reacting with a transition metal in a metal compound such as those disclosed in JP-A Nos. 2000-191862 and 2002-097325, organoaluminum compounds, and aluminoxanes A method of polymerizing propylene in the presence of a metallocene catalyst comprising:

(Olefin / polyene copolymer)
The (Z) olefin / polyene copolymer, 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 the α-olefin 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. Among these, preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, particularly preferably propylene, 1-butene, 1-hexene, 4-methyl-1- Pentene 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-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene (5-vinylbicyclo [2.2.1] hept-2-ene ), Dicyclopentadiene, 2-methyl-1,4-hexadiene, 2-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, Examples include 5,9-dimethyl-1,4,8-decatriene. Among these, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, butadiene, isoprene, 2-methyl-1,4-hexadiene or 2-methyl-1,6-octadiene is preferable. Vinyl norbornene is particularly preferable because it has a bulky skeleton, so that the wax can be hardened even at a low density and the wax product is hardly blocked.

  (Z) The olefin / polyene copolymer is a copolymer of ethylene and polyene, a copolymer of ethylene and at least one α-olefin selected from α-olefins having 3 to 12 carbon atoms and polyene. Preferably there is.

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

  When the (Z) olefin / polyene copolymer in the present embodiment contains structural units derived from polyene in a proportion within the above range, the polymerization activity is also moderately high.

  In addition, when a structural unit derived from an α-olefin having 3 to 12 carbon atoms is contained in a proportion within the above range, a rubber layer having less surface tackiness and excellent mechanical properties and impact properties can be obtained.

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

In addition, the unsaturated group content of the (Z) olefin / polyene copolymer is measured as follows. ^The number M of unsaturated groups per 1,000 carbons can be obtained by comparing the peak area of the carbon of the unsaturated portion by ¹³ C-NMR with the peak area of the total carbon. 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 M of unsaturated groups per 1,000 carbons is 1.4 to 105, preferably 1.4 to 70, and more preferably 2.8 to 70.

(Z3) in the embodiment (Z) olefin-polyene copolymer, 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, And it is preferable that it is 980 kg / m < ³ > or less, Preferably it is 970 kg / m < ³ > or less, More preferably, it is 960 kg / m < ³ > or less. (Z) When the density of the olefin / polyene copolymer is within the above range, there is little tackiness and excellent dispersibility in the rubber layer, so that a rubber layer having excellent scratch resistance and durability is obtained. Can do.

  (Z4) The (Z) olefin / polyene copolymer in this embodiment has a melting point measured by a differential scanning calorimeter (DSC) of 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably It is preferably 100 ° C. or higher and 130 ° C. or lower, preferably 125 ° C. or lower, more preferably 120 ° C. or lower. (Z) When the melting point of the olefin / polyene copolymer is within the above range, there is little tackiness and excellent dispersibility in the rubber layer, thereby obtaining a rubber layer having excellent scratch resistance and durability. Can do.

  (Z5) The (Z) olefin / polyene copolymer in this embodiment has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000, preferably 400 to 4,000, More preferably, it is in the range of 400 to 3,000, particularly preferably 1,500 to 2,500. (Z) When Mn of the olefin / polyene copolymer is within the above range, there is little tackiness and excellent dispersibility in the rubber layer, so that a rubber layer having excellent scratch resistance and durability can be obtained. Can do.

  (Z6) The (Z) olefin / polyene copolymer in this 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.

  In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are polystyrene conversion 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 (Z) olefin / polyene copolymer in the present embodiment has a penetration 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 dmm or less. It is preferable. The penetration hardness can be measured according to JIS K2207. (Z) When the penetration hardness of the olefin / polyene copolymer is within the above range, a rubber layer having excellent scratch resistance and durability can be obtained.

The (Z) olefin / polyene copolymer in the present embodiment includes the (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) penetration hardness, more preferably two or more, and still more preferably three or more. It is even more preferable that the above is satisfied, it is particularly preferable that five or more are satisfied, and it is particularly preferable that all six are satisfied. For example particularly preferred embodiment is 0.5 to 3.0 groups / molecule unsaturated group content (Z2-1), (Z3-1) density of 870~980kg / m ^3, (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. More preferably, in addition to these five (Z7-1), the penetration hardness satisfies 15 dmm or less.

The (Z) olefin / polyene copolymer according to the present embodiment is copolymerized using vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) as a polyene. In some cases, the (Z) olefin / polyene copolymer 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) penetration hardness, more preferably two or more, and still more preferably three or more. It is even more preferable that the above is satisfied, it is particularly preferable that five or more are satisfied, and it is particularly preferable that all six are satisfied. For example particularly preferred embodiment is 0.5 to 2.0 groups / molecule is (Z2-2) unsaturated group content, (Z3-2) density of 890~980kg / m ^3, (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. More preferably, in addition to these five, (Z7-2) those satisfying a penetration hardness of 15 dmm or less are mentioned.

  The (Z) olefin / polyene copolymer as described above is composed of, for example, a metallocene compound of a transition metal selected from Group 4 of the periodic table and an organoaluminum oxy compound and / or an ionized ionic compound as shown below. It can manufacture using a system catalyst. Suitable metallocene catalysts in the present embodiment include Japanese Patent Application Laid-Open No. 2001-002731 or PCT applications already published internationally, WO / 2007/114102, WO / 2007/1055483, WO / 2007/114409, WO / 2007. For example, (A) transition metal metallocene compounds selected from Group 4 of the periodic table, and (B) (b-1) organoaluminum oxy compounds, (b-2) metallocene compounds (A And an olefin polymerization catalyst comprising at least one compound selected from (b-3) an organoaluminum compound.

Specific examples of (A) metallocene compounds of transition metals selected from Group 4 of the periodic table in this embodiment include bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, and bis. (1-Methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethyl ((t-butylamide) (tetramethyl-η ⁵ -Cyclopentadienyl) silane) titanium dichloride and the like.

  In addition, (B) (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound in this embodiment. Specific examples of at least one selected compound include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3 , 5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, 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 of excellent wear resistance and durability and less bleed and bloom from the rubber layer surface.

  The silylated polyolefin used in the present embodiment can be produced by any method, but preferably the silylated polyolefin obtained by sequentially performing the following [Step 1] and [Step 2]. Or a derivative thereof, or a mixture thereof.

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

  Below, the manufacturing method of silylated polyolefin is explained in full detail.

[Step 1]: Step of obtaining a transition metal catalyst composition (C) In [Step 1], a silicon-containing compound and a transition metal halide are mixed and stirred, and the resulting suspension solution is filtered to obtain a transition metal as a filtrate. A catalyst composition (C) is obtained.

  The halogenated transition metal is a halide of a transition metal from Group 3 to Group 12 of the periodic table, and preferably from Group 8 to Group 10 of the periodic table from the viewpoint of availability and economy. More preferred are halides of platinum, rhodium, iridium, ruthenium, osmium, nickel and palladium. More preferred is a platinum halide. Further, it may be a mixture of two or more transition metal halides.

  Examples of the halogen of the halogenated transition metal include fluorine, chlorine, bromine, and iodine. Among these, chlorine is preferable from the viewpoint of easy handling.

  Specific examples of the transition metal halide used in [Step 1] include platinum dichloride, platinum tetrachloride, platinum dibromide, platinum diiodide, rhodium trichloride, rhodium tribromide, rhodium triiodide, three Iridium chloride, iridium tetrachloride, iridium tribromide, iridium triiodide, ruthenium trichloride, ruthenium tribromide, ruthenium triiodide, osmium trichloride, osmium tribromide, osmium triiodide, nickel dichloride, two 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 preferred, and platinum dichloride is most preferred.

  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. As the particle size increases, the preparation time of the transition metal catalyst composition (C) becomes longer.

  The amount of the silicon-containing compound and the transition metal halide 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 transition metal halide, but preferably 2 equivalents or more. When the amount of the silicon-containing compound is small, stirring necessary for preparing the transition metal catalyst composition (C) becomes difficult.

  The mixing and stirring of the silicon-containing compound and the transition metal halide in [Step 1] is not limited as long as this is possible, but an appropriate amount of the transition metal halide is charged into a reaction vessel equipped with a stirrer under a nitrogen stream. Then, a silicon-containing compound is added thereto and stirred. In the case of a small amount, a stirrer chip may be put in a sample tube and charged in the same manner and stirred.

  The mixing and stirring time of the silicon-containing compound and the transition metal halide is not particularly limited, but is usually 10 hours or longer, preferably 20 hours or longer, more preferably 60 hours or longer, and further preferably 80 hours or longer. It is. If the reaction time is short, the production rate of the isomeric vinylene derivative which is an impurity in the silylated polyolefin obtained in the next [Step 2] increases, which is not preferable. Although there is no particular upper limit for the mixing and stirring time, it is generally within one month from an economical viewpoint.

  The temperature of mixing and stirring the silicon-containing compound and the transition metal halide is not particularly limited as long as it is not higher than 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. In addition, the pressure can be usually performed at normal pressure, but can be performed under pressure or under reduced pressure as necessary.

  In [Step 1], a solvent may be used as necessary. As the solvent to be used, those inert to the silicon-containing compound and the transition metal halide can be used. Specific examples of the solvent 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, acetone, Examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and methyl propyl ketone; ethers such as tetrahydrofuran and 1,4-dioxane; 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 weight or less, more preferably 20 times by weight or less based on the raw material. In this embodiment, it is most preferable to carry out without a solvent.

  Next, the suspended solution obtained by the reaction is filtered to remove solids, and a transition metal catalyst composition (C) is obtained as a filtrate. There is no restriction | limiting in particular as a filtration method, General methods, such as natural filtration, pressure filtration, and reduced pressure filtration, can be used. There is no restriction | limiting in particular as a filter used by filtration, The membrane filter made from a cellulose filter paper, a glass fiber filter, a fluororesin, or a cellulose acetate etc. can be used suitably. Among these, it is preferable to use a fluororesin membrane filter in view of uniformity of pore diameter, low hygroscopicity, chemical stability, and the like. The filter used for filtration is preferably an eye filter smaller than 10 μm, and more preferably an eye filter of 1 μm or less. If a larger filter than this is used, the solid content of the unreacted transition metal halide is mixed in the catalyst and the catalyst becomes heterogeneous, which increases the amount of vinylene derivative that is an impurity of the synthesis target. Cause. Further, during filtration, the solid content can be washed using the above-mentioned solvent.

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

  The transition metal catalyst composition (C) thus prepared contains a transition metal compound in a nanocolloid form, 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 is used in [Step 2] after removing the solvent, concentrating and diluting as necessary. You can also Further, the catalyst concentration can be adjusted by further diluting the silicon-containing compound.

  Instead of carrying out [Step 1], a commercially available transition metal catalyst, for example, platinum alone (platinum black), chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, or a platinum carrier on a carrier such as alumina or silica. Although what was carry | supported is mentioned, You may use this for [process 2].

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

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

  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 to the Si-H bond in the silicon-containing compound is 0.01 to It is the range of 10, Preferably it is the range of 0.1-2. Here, the amount of the silicon-containing compound is the total amount of the portion used in [Step 1] and included in the transition metal catalyst composition (C) and the portion newly added in [Step 2]. When the total amount of the silicon-containing compound required in [Step 1] is used, the [Step 2] can be carried out without adding a silicon-containing compound.

The reaction between the vinyl group-containing compound and the silicon-containing compound is performed 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 component in the transition metal catalyst composition (C). Is in the range of -10 ^-1 , preferably in the range of 10 ^-7 to 10 ^-3 .

  As a reaction method in the reaction between the vinyl group-containing compound and the silicon-containing compound, it may be finally reacted, and the method is not limited. For example, the reaction is performed as follows. A vinyl group-containing compound is charged into a reaction vessel, and a silicon-containing compound and a transition metal catalyst composition (C) are charged under a nitrogen atmosphere. The reactor is set and stirred in an oil bath whose internal temperature has been raised to the melting point of the vinyl group-containing compound in advance. After the reaction, the oil bath is removed and the reaction mixture is cooled to room temperature. The resulting reaction mixture is taken out in a poor solvent such as methanol or acetone and stirred for 2 hours. Thereafter, the obtained solid is collected by filtration, washed with the above poor solvent, and dried under reduced pressure at 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 performed at a reaction temperature in the range of 100 to 200 ° C., more preferably at a temperature higher than the melting point of the vinyl group-containing compound to be reacted. . A reaction temperature lower than 100 ° C. is not preferable because the reaction efficiency may be lowered. In addition, the pressure can be usually performed at normal pressure, but can be performed under pressure or under reduced pressure as necessary.

  In [Step 2], a solvent may be used as necessary. As the solvent to be used, those inert to the silicon-containing compound and the vinyl group-containing compound as raw materials can be used. When making it react under a normal pressure, it is preferable to use what has a boiling point more than melting | fusing point of the vinyl group containing compound to react. Specific examples of the solvent that can be used include aliphatic hydrocarbons such as n-hexane and decane, alicyclic hydrocarbons such as cyclohexane and cycloheptane, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, acetic acid, and the like. Esters such as butyl, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and methyl propyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, perchloroethane, etc. Examples thereof 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 based on the raw material. In this embodiment, it is most preferable to carry out without a solvent.

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

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

  The ratio of the structure derived from the structural unit represented by the above formula (1) in the silylated polyolefin is not particularly limited as long as the target function of the silylated polyolefin is expressed, but is usually 5 to 99% by weight. Yes, preferably 10 to 95% by weight. If the structural unit is in this range, scratch resistance and durability functions can be exhibited, and the oil is less likely to bleed out from the rubber layer.

  In the above method, since the transition metal catalyst composition (C) having a very high activity and selectivity obtained in [Step 1] is used, the vinyl group-containing compound and the silicon-containing compound in [Step 2] are used. The reaction proceeds efficiently. For this reason, 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 vinylene derivative produced as a by-product is usually 10 wt. % Or less, preferably 5% by weight or less.

  Silylated polyolefin can be removed from the reaction mixture by reprecipitation in a poor solvent or by sludgeing. The poor solvent is not particularly limited as long as the solubility of the silylated polyolefin is small, and can be appropriately selected. Specific examples of the poor solvent include acetone, methanol, ethanol, n-propanol, isopropanol, acetonitrile, ethyl acetate, n-hexane, and n-heptane. Among these, acetone and methanol are preferable.

  The resulting silylated polyolefin has a melt mass flow rate (MFR) measured at 190 ° C. and a load of 2.16 kg according to the method of JIS K7210, 0.01 g / 10 min or more, preferably 0.1 g / 10 min or more. More preferably, it is 1.0 g / 10 min or more. There is no particular upper limit. This index is an index indicating that the silylated polyolefin has not undergone crosslinking or the like that impairs the fluidity of the resin.

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

A-CH = CH ₂ (4)
(In the above formula (4), A is a polymer chain containing a structural unit derived from one or more 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 in which A is composed only of an α-olefin having 2 to 20 carbon atoms (structure 4-1) is preferable.

More preferably, the vinyl group-containing compound has a structure (Structure 4-2) in which —CH═CH ₂ is present at the terminal of the polymer main chain.

Even more preferably, the vinyl group-containing compound has a structure (structure 4-3) in which —CH═CH ₂ is present only at the terminal of the polymer main chain.

Still more preferably, the vinyl group-containing compound has a structure (structure 4-4) (structure 4) in which A is composed only of an α-olefin having 2 to 20 carbon atoms, and —CH═CH ₂ is present at the terminal of the polymer main chain. -1 and the structure 4-2).

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

  When the vinyl group-containing compound is a (Z) olefin / polyene copolymer, a structure using vinyl norbornene as the polyene is more preferable.

  As described above, the silicon-containing compound of the present embodiment specifically has a 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 of (Z) the structure of the olefin / polyene copolymer 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). 2) A structure (structure 2-2) in which R ⁴¹ in Z in Z is all selected from a hydrocarbon group and a halogen is more preferable (that is, R ⁴¹ is preferably not a hydrogen atom).
Further, in the case where the vinyl group-containing compound is a (Z) olefin / polyene copolymer, for example, when there are 2.0 or more vinyl groups on average per molecule, In (2), m = 1, n = 0, and R ⁴¹ in Z in the above formula (2) is a structure selected from a hydrocarbon group and a halogen (structure 2-3), or A compound having a structure (structure 2-4) in which m = 0 and n = 0 in formula (2) and only one of R ⁴¹ in Z in formula (2) is a hydrogen atom is preferable.

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

  Silylated polyolefin and its derivatives are presumed to have a structure represented by, for example, 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.

(M, n, o, p, q in the above formulas represent an integer of 1 or more.)
Below, a particularly preferable aspect and the reason for the estimation will be described. Hereinafter, the part derived from the vinyl group-containing compound may be referred to as “polyolefin chain”, and the part derived from the silicon-containing compound may be referred to as “silicon-containing compound chain”. When the vinyl group-containing compound has the structure represented by the above formula (4), particularly the structure (4-5) and the silicon-containing compound has the structure (2-2), the silylated polyolefin has (polyolefin chain)- It is considered to have a structure like a block copolymer in which (silicon-containing compound chain)-(polyolefin chain) are bonded in this order. Specifically, the compound which has a presumed structure like above-mentioned Formula (5) can be illustrated.

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

  In addition, when the vinyl group-containing compound has the structure (4-5) and the silicon-containing compound has the structure (2-3) and the structure (2-4), the silylated polyolefin can be expressed by the above formula. (6) It is thought that it has taken the structure like Formula (8).

Further, the vinyl group-containing compound has the structure (4-5), and the silicon-containing compound is m = 0, n = 0, and Z is (—SiH (CH ₃ ) O—) ₆ —Si (CH ₃ ) In the case of ₂ O—Si (C ₆ H ₅ ) ₂ —, it is considered that it may take the form of the formula (7).

  When the vinyl group-containing compound is a (Z) olefin / polyene copolymer and the silicon-containing compound has the structure (2-3), the silylated polyolefin grafts (silicon-containing compound chain) to (polyolefin chain). Therefore, it is thought that the structure as in the above formula (9) may be taken.

  A vinyl group presumed to have the structure of a block copolymer of (polyolefin chain)-(silicon-containing compound chain)-(polyolefin chain), for example, 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 thought that it is easy to carry out molecular motion than the silylated polyolefin estimated. Therefore, for example, it is considered that the silylated polyolefin is more likely to collect on the surface of the molded body by high-temperature crosslinking using a mold. In addition, with the above structure, polyolefin chains are present at both ends of the silicon-containing compound chain, and therefore it is considered that there is little bleed out or bloom out from the rubber layer surface.

(Filler (C))
Unlike carbon black such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT, filler (C), which is one of the components contained in the composition according to the present invention, has the following requirements (C- As long as 1) is satisfied, those usually used as a reinforcing material for synthetic rubber can be used. The filler (C) preferably satisfies the following requirements (C-1) to (C-2).

・ Requirement (C-1)
The filler usually has an average particle size of 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 diameter means a 50% equivalent particle diameter d50 obtained from an integral distribution curve measured using a laser diffraction particle size distribution measuring device (a particle size distribution measuring device based on a laser diffraction / scattering method). .

  As filler (C), silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine talc, fine silicate, talc, clay, calcium silicate, kaolin, talc, diatomaceous earth, mica powder, asbestos, Alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, glass balloon, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, etc. The inorganic surface treated with a silane coupling agent or the like can be used. Considering the use of rice threshing, it is not preferable to use fillers with black color such as carbon black or color, and fillers with white color tone such as silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, etc. preferable. Among these, silica is more preferable from the viewpoint that excellent dispersibility can be obtained and wear resistance of carbon black and identification degree can be obtained.

・ Requirement (C-2)
Although the specific surface area of a filler (C) is not specifically limited as long as there exists an effect of this invention, it is preferable that it is 5-120 m < ² > / g. In the present invention, silica can be preferably used because of the effect of improving rigidity.

〔Composition〕
The composition according to the present invention comprises 0.01 to 100 parts by weight of a total of silylated polyolefin and / or a derivative thereof (β) with respect to 100 parts by weight of the rubber component (α) and the rubber component (α). Preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight and 100 parts by weight of the rubber component (α) for the reason that the optimum value of threshing property is obtained. 100 to 100 parts by weight, preferably 30 to 100 parts by weight, more preferably 40 to 100 parts by weight for the reason that high hardness can be achieved.

  When each component is in the above range, the composition has improved dispersibility of fillers, particularly silica, with respect to rubber, and has good moldability. A rubber layer made of the composition is preferable because it is very excellent in wear resistance and durability and can be used for a long time.

  If the amount of the silylated polyolefin and / or its derivative (β) is less than 0.01 parts by weight, the durability and wear resistance of the rubber layer may not be obtained. If the amount of the silylated polyolefin and / or derivative (β) exceeds 100 parts by weight, threshing may not be possible.

  If the blending amount of the filler (C) is less than 1 part by weight, the desired effect cannot be obtained, and the rubber layer obtained by vulcanization may have poor rigidity and mechanical strength. If the blending amount of the filler (C) exceeds 100 parts by weight, the kneadability is poor, and the rubber elasticity and mechanical strength of the rubber layer obtained by vulcanization may be lowered.

  When the rubber component (α) contains the copolymer (A) and the copolymer (B), the copolymer (A) is usually 0 to 99 parts by weight, preferably 0 to 90 parts by weight. Parts, more preferably 0 to 60 parts by weight, still more preferably 0 to 50 parts by weight for workability reasons, and the copolymer (B) is usually 1 to 100 parts by weight, preferably 10 to 100 parts by weight. Parts, more preferably 40 to 100 parts by weight, and even more preferably, 50 to 100 parts by weight (provided that the copolymer (A) and The total of the copolymer (B) is 100 parts by weight). Moreover, in this case, the composition usually contains 1 to 100 parts by weight, preferably 30 parts, of the filler (C) with respect to 100 parts by weight in total of the copolymer (A) and the copolymer (B). It is preferable to contain 40-100 weight part from the reason for achieving ~ 100 weight part, More preferably high hardness.

  A composition in which the blending amount of the copolymer (B) is less than 1 part by weight may not provide sufficient wear resistance.

  When the copolymer (A) having a medium ethylene content is blended, it is preferable because the processability is excellent.

  In the case where the copolymer (A) and the copolymer (B) are contained, the composition having a filler (C) content of less than 1 part by weight cannot obtain a desired effect and is obtained by vulcanization. There is a possibility that the rigidity and mechanical strength of the rubber layer to be produced are inferior. A composition in which the blending amount of the filler (C) exceeds 100 parts by weight has poor kneading workability, and there is a risk that the rubber elasticity, mechanical strength, etc. of the rubber layer obtained by vulcanization will be lowered.

  It is preferable to include the copolymer (B) because the rubber layer has higher hardness.

  In the composition containing the copolymer (A) and the copolymer (B) as the rubber component (α), the dispersibility of the farer (C) in the composition is remarkably improved, and the moldability is further improved. Will also improve. Therefore, the rubber layer made of the composition has not only high hardness but also excellent wear resistance and durability due to good dispersion of the filler (C). By using the rubber layer on the surface of the hulling roll, a hulling roll that is excellent in wear resistance, excellent in durability, and can be used over a long period of time can be more suitably obtained.

  According to this invention, the threshing machine for agriculture provided with this hulling roll is obtained suitably.

(Crosslinking agent (D))
In addition to the rubber component (α), silylated polyolefin and / or derivative thereof (β) and filler (C), the composition according to the present invention may contain a crosslinking agent (D). Examples of the crosslinking agent used for crosslinking include vulcanizing agents such as sulfur and sulfur compounds, and organic peroxides. The cross-linking agent is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 5 parts per 100 parts by weight of the rubber component (α). It mix | blends in the ratio of a weight part.

  In the present invention, a vulcanizing agent is preferred because it has less odor than organic peroxides and is excellent in workability and can be processed satisfactorily.

-Vulcanizing agent As one of the crosslinking agents, sulfur and a sulfur compound are mentioned as a vulcanizing agent used in vulcanization. Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.

  Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, and polymer polysulfide. Also use sulfur compounds that release active sulfur at the vulcanization temperature, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, selenium dimethyldithiocarbamate. Can do. Of these, sulfur is preferably used. These sulfur and sulfur compounds are used alone or in combination of two or more.

  Sulfur and the sulfur compound are not particularly limited as long as the effects of the present invention are exerted, but usually 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the rubber component (α). More preferably, it is used in a proportion of 0.3 to 5 parts by weight, but it is desirable to determine the optimum amount appropriately according to the required physical properties. Moreover, when using sulfur and a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator together.

・ Vulcanization accelerator Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolsulfenamide, N, N-diisopropyl-2- Sulfenamide compounds such as benzothiazol sulfenamide; 2-mercaptobenzothiazole, 2- (2 ′, 4′-dinitrophenyl) mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole, di-2 -Thiazole compounds such as dibenzothiazyl disulfide (MBTS); guanidine compounds such as diphenylguanidine, diorthotolylguanidine, diorthonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant, butyraldehyde Aniline condensate, hexamethylene Aldehyde amines or aldehyde-ammonia compounds such as tetramine and acetaldehyde ammonia; imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; Thiuram compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate ( ZnBDC), zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, dimethyl Examples include dithioate compounds such as sodium rudithiocarbamate, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate; xanthates such as zinc dibutylxanthate; and compounds such as zinc white (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 with respect to 100 parts by weight of the rubber component (α). However, it is desirable to appropriately determine the optimum amount according to the required physical properties.

-Organic peroxide The organic peroxide that is one of the crosslinking agents may be any one that is usually used for rubber peroxide vulcanization. Specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, benzoyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-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. 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 the effects of the present invention are exhibited, but is usually 0.0003 to 0.05 mol, preferably 0.001 to 0.03, relative to 100 parts by weight of the rubber component (α). Although it is used in a molar ratio, it is desirable to appropriately determine the optimum amount according to the required physical properties.

  When using an organic peroxide as a crosslinking agent, it is preferable to use a crosslinking aid in combination. Specific examples of crosslinking aids 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; Maleimide compounds; divinylbenzene and the like. Such a crosslinking aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, with respect to 1 mol of the organic peroxide used.

(Other ingredients)
The composition according to the present invention includes various known additives generally used in the manufacture of rubber products, such as softeners, anti-aging agents, processing aids, alkoxysilane compounds, activators, depending on performance. , Reaction inhibitors, colorants, dispersants, flame retardants, plasticizers, antioxidants, scorch inhibitors, UV absorbers, antistatic agents, lubricants, antifungal agents, peptizers, tackifiers, surfactants An agent or the like may be selected as appropriate and blended in an appropriate amount.

-Softener As a softener, the softener normally used for rubber | gum can be used.

  Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fat 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 ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; petroleum Examples thereof include synthetic polymer materials such as resin, atactic polypropylene, and coumarone indene resin. Of these, petroleum softeners are preferably used, and process oil is particularly preferably used.

  The blending amount of these softening agents is not particularly limited as long as the effects of the present invention are exhibited, but it is 150 parts by weight or less, preferably 130 parts by weight or less, with respect to 100 parts by weight of the rubber component (α).

-Anti-aging agent If an anti-aging agent is used, it is possible to further extend the life of the material. This is the same as in the case of ordinary rubber.

  Specific examples of the antioxidant 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] phenol stabilizers such as methane; thioether stabilizers such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide; 2-mercaptobenzimidazole, etc. Benzoimidazole stabilizers; dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate; quinoline stabilizers such as a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline. These anti-aging agents are used alone or in combination of two or more.

  Such an anti-aging agent is not particularly limited as long as the effect of the present invention is exhibited, but is usually 5 parts by weight or less, preferably 3 parts by weight or less with respect to 100 parts by weight of the rubber component (α). However, it is desirable to appropriately determine the optimum amount according to the required physical property value.

-Processing aid As a processing aid, the compound used for normal rubber processing can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid, higher fatty acid salts such as barium stearate, zinc stearate and calcium stearate, ricinoleic acid ester, stearic acid ester, palmitic acid ester and lauric acid And higher fatty acid esters such as acid esters.

  Such processing aids are not particularly limited as long as the effects of the present invention are exhibited, but are usually used in a proportion of 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the rubber component (α). However, it is desirable to appropriately determine the optimum amount according to the required physical property value.

-Surfactant As a surfactant, the compound used for normal rubber processing can be used. Specifically, amines such as di-n-butylamine, dicyclohexylamine, monoelaanolamine, triethanolamine, “Acting B (manufactured by Yoshitomi Pharmaceutical Co., Ltd.),“ Acting SL (manufactured by Yoshitomi Pharmaceutical Co., Ltd.), polyethylene glycol , Zinc compounds of diethylene glycol, polyethylene glycol, lecithin, triarylutemelite, aliphatic and aromatic carboxylic acids (e.g., "Struktol activator 73", "Struktol IB 531", "Struktol FA541" Schill & Seilacher ON ET "P") (Nippon Zeon Co., Ltd.), octadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds (eg, “Arcade 2HF” (Rai On Akzo Corporation).

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

[Production Method of Composition]
The composition according to the present invention comprises the rubber component (α), the silylated polyolefin and / or its derivative (β), the filler (C), and, if necessary, the crosslinking agent (D), for example, a softener, etc. In general, it can be prepared from various known additives used in the manufacture of rubber products by a general method for manufacturing a rubber compound.

  As a method for producing the composition, for example, the rubber component (α), silylated polyolefin and / or a derivative thereof (β), using an internal mixer (closed mixer) such as a Banbury mixer, a kneader, or an intermix, The filler (C) and, if necessary, a softening agent (for oil expansion), a processing aid, a vulcanization accelerator and the like are kneaded at a temperature of 80 to 170 ° C. for 2 to 20 minutes. Then, if necessary, a vulcanization accelerator is added to the resulting blend using additives such as a cross-linking agent (D) and a softening agent, using rolls such as open rolls, or a kneader. It can be prepared by further mixing a crosslinking aid, kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and dispensing.

  Therefore, the composition (unvulcanized compounded rubber) according to the present invention is prepared, for example, by the following method. By rubber mixers, kneaders, internal mixers such as intermix, the rubber component (α), silylated polyolefin and / or derivatives thereof (β), and filler (C), if necessary, softener, processing After kneading additives such as auxiliaries and vulcanization accelerators at a temperature of 110 to 170 ° C. for 3 to 10 minutes, using a roll such as an open roll or a kneader, if necessary, a crosslinking agent ( D) A softening agent, a vulcanization accelerator, or a vulcanization aid is additionally mixed at a temperature of less than 120 ° C., kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then prepared by dispensing. Can do.

  Further, when the kneading temperature in the internal mixer is low, the rubber component (α), silylated polyolefin and / or derivative thereof (β), and filler (C) together with a softening agent, if necessary, A crosslinking agent (D), a vulcanization accelerator, a vulcanization auxiliary agent, or the like can be kneaded at the same time.

[Rubber layer]
The rubber layer according to the present invention is composed of the composition. Moreover, it is preferable that this rubber layer consists of the crosslinked material which bridge | crosslinked this composition in presence of the crosslinking agent (D). In particular, when the rubber layer is made of a vulcanized product, ion agglomerates are formed in the rubber layer, so that the rubber layer has high rigidity, excellent mechanical properties (extensibility) and rubber elasticity. Have both. Therefore, it is particularly preferable since the rubber layer can be thinned to have desired physical properties (particularly wear resistance and durability).

  The rubber layer is not particularly limited as long as the effect of the present invention is exhibited, but it is preferable that the durometer A hardness measured in accordance with JIS K6253 is 10 to 100. When the durometer A hardness is less than 10, the rubber layer is too soft and wear resistance may be lowered. On the other hand, if the durometer A hardness exceeds 100, the rice may be damaged at the time of scouring, and the occurrence rate of so-called broken rice may be increased.

  The durometer A hardness is more preferably from 40 to 100, and more preferably from 60 to 100 from the viewpoint of the balance between the breaking rate of rice and the wearability.

  The durometer A hardness of the rubber layer is preferably about 40 to 90 when the rice to be hulled is relatively soft japonica rice or the like, and when the rice to be hulled is relatively hard indica rice or the like. About 60-100 is preferable.

  The “rubber layer” in the present invention corresponds to the “rubber part” referred to in JIS K 9124.

  The rubber layer preferably has a tan δ peak temperature (Tg) of 10 ° C. or less. This is because appropriate rubber elasticity is exhibited at 30 to 50 ° C., which is the temperature of the rubber layer during use.

  The rubber layer preferably has a DIN wear amount of 10 to 500 mg. If the DIN wear amount is less than 10 mg, the occurrence rate of broken rice may be high at the time of scouring, 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.

  The thickness of the rubber layer is not particularly limited as long as the effects of the present invention can be obtained, and can be appropriately set according to the specifications of the hulling machine to which the hulling roll is attached and the JIS standard (JIS B 9214) as in the conventional product. Here, the thickness of the rubber layer means a value that is ½ of the difference between the outer diameter and the inner diameter of the rubber layer when not in use.

[Method for producing rubber layer]
The rubber layer is formed by injection-molding and crosslinking the rubber composition in a mold in which the core part of the rice roll is set in advance.

  The rubber layer is prepared by once preparing an uncrosslinked composition (compounded rubber) by the method described above, and then molding the blended rubber into the intended shape, in the same manner as when ordinary rubber is crosslinked. It can also be obtained by carrying out crosslinking after this. As crosslinking, vulcanization is preferred.

  The uncrosslinked composition prepared as described above can be molded and crosslinked by various molding methods such as an extruder, a calender roll or a press, but it can be used for compression molding, injection molding, injection molding, etc. When molding and crosslinking, the characteristics can be exhibited most by mold molding.

  That is, in the case of compression molding, a pre-weighed uncrosslinked compounded rubber is put into a mold, and after closing the mold, it is heated at a temperature of 120 to 270 ° C. for 30 seconds to 120 minutes. can get.

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

  In the case of injection molding, a pre-weighed compounded rubber is placed in a pot and injected into the mold by a piston in 1 to 20 seconds. After injecting the compounded rubber, the target crosslinked rubber layer is obtained by heating at a temperature of 120 to 270 ° C. for 30 seconds to 120 minutes.

[Coffin roll]
The hulling roll of the present invention has the rubber layer on the surface of the core part. Usually, the hulling roll is obtained by baking a rubber layer on the surface of the core part and then subjecting the surface to polishing or finishing. As the core material portion, for example, a core material portion used in a conventionally known hulling roll such as a metal fitting drum can be used. Examples of the material of the core part include aluminum, stainless steel, iron, molybdenum, and titanium. Moreover, the shape and size of the core part are not particularly limited, and can be appropriately set according to the specifications of the hulling machine to which the hulling roll is attached and the JIS standard (JIS B 9214: rubber roll for rice hulls) as in the conventional product.

  In the hulling roll of the present invention, a primer layer and / or an adhesive layer may be formed between the core material part and the rubber layer in order to further improve the adhesion. Moreover, you may perform the surface treatment for improving adhesiveness with this rubber layer to the outer peripheral surface of a core material part. The formation of the adhesive layer is not particularly limited as long as the effects of the present invention are exhibited, but can be performed using, for example, a phenol-based adhesive or the like. In addition, the formation of the primer layer is not particularly limited as long as the effects of the present invention are exhibited. For example, the primer layer may be formed using a urethane-based, polyester-based, silane-based, polyamide-based, phenol-based primer, a silane coupling agent, or the like. Can do. Examples of the surface treatment include formation of a roughened surface, and the roughened surface may be formed by, for example, blast treatment, grinding treatment, etching treatment, plating treatment, polishing treatment, oxidation treatment, or the like.

  The hulling roll preferably has a roundness of 0.5 mm or less in its cross section (cross section perpendicular to the rotation axis in use). When the roundness exceeds 0.5 mm, the variation in the spacing between the hulling rolls during use increases, and the removal rate may decrease or the occurrence rate of broken rice may increase.

  Moreover, according to this invention, the threshing machine for agriculture provided with this hulling roll is obtained suitably.

[Manufacturing method of hulling roll]
The hulling roll can be manufactured, for example, through the following steps (1) and (2).

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

  (2) Next, the rubber layer is formed around the core part. As a forming method, for example, the core part is placed in a cylindrical mold, and then the composition is injected into the gap between the outer peripheral surface of the core part and the inner wall surface of the mold, and cured under predetermined conditions. By doing so, a rubber layer can be formed. The above-mentioned can refer to this condition.

  Curing conditions are not particularly limited as long as the effects of the present invention are exhibited, and can be set as appropriate. However, conditions of heating at 100 to 160 ° C. for 30 to 90 minutes can be employed. Moreover, after performing a hardening process and removing from a metal mold | die, you may postcure on the conditions for 3 to 48 hours at 100-160 degreeC, for example.

  Since the dispersibility of the filler is remarkably improved and the composition according to the present invention has suitable moldability, the composition can be suitably laminated on the surface of the core part. Therefore, according to the present invention, a hulling roll having a rubber layer that has a uniform density over the entire surface of the core part, is excellent in wear resistance and durability, and can be used over a long period of time. It can manufacture suitably.

  In the hulling roll manufacturing method, the surface of the rubber layer may be formed by grinding as necessary. Grinding may not be performed while being removed from the mold.

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

  The pair of hulling rolls are normally attached to the hulling machine in parallel so as to have a predetermined interval, and rotate each of the hulling rolls in opposite directions and at different rotational speeds. In addition, when rice bran is introduced between the hulling rolls in this state, the rice husk is removed from the rice hulls due to the difference in peripheral speed between the hulling rolls.

  The distance between the hulling rolls and the rotation speed (circumferential speed) of each hulling roll are not particularly limited, depending on the specifications of the hulling machine, the type and drying rate of the rice to be fed, the drying rate, the processing speed, the removal rate, etc. What is necessary is just to set suitably.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.

(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 Number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were measured as follows using GPC-150 manufactured by Millipore. That is, the separation column was TSK GNH HT, and the column size was 7.5 mm in diameter and 300 mm in length. The column temperature was 140 ° C., orthodichlorobenzene (manufactured by Wako Pure Chemical Industries) was used as the mobile phase, and 0.025% by mass of BHT (manufactured by Takeda Pharmaceutical) was used as the antioxidant, and the mobile phase 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 a detector. A calibration curve was prepared using standard polystyrene and converted into a value in terms of polyethylene according to a conventional method.

  In the following synthesis examples, the number of moles of the raw material polymer is represented by a value based on (Mn).

[M2] Melting point measurement method The peak top temperature obtained by measurement using DSC was adopted as the melting point (Tm). The apparatus used was a DSC-60A manufactured by Shimadzu Corporation. The control cell used alumina and the nitrogen flow rate was set at 50 ml / min. Moreover, it measured on the temperature rising conditions from 30 degreeC to 300 degreeC at 10 degree-C / min. 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 heat history of the resin. It is preferable.

[M3] Yield, conversion rate, isomerization rate, terminal unsaturation measurement and calculation method by NMR analysis The yield, conversion rate, isomerization rate, and terminal unsaturation rate of silylated polyolefin are determined by ¹ H-NMR. Is done. Yield is the ratio of the number of moles of the silylated polyolefin obtained relative to the number of moles of the vinyl group-containing compound as the raw material, and the conversion ratio is the ratio of the same number of moles consumed relative to the number of moles of the vinyl group-containing compound as the raw material. Is the ratio of the number of moles of vinylene produced to the number of moles of the vinyl group-containing compound of the raw material, and the terminal unsaturation is the main chain with respect to the total of the terminal vinyl group and terminal methyl group of the main chain of the vinyl group-containing compound as the raw material It is defined as the proportion of terminal vinyl groups. The terminal unsaturation rate and the number of vinyl groups per thousand carbons are generally applied to the vinyl group-containing compound that is the raw material, but when hydrosilylation is not sufficient, etc., an indicator of the remaining amount of unreacted raw material May also be applied to silylated polyolefins.

  For example, a peak (C) of 6 protons of ethoxy group methylene of a silylated polyolefin obtained by hydrosilylating a main chain terminal vinyl group-containing compound consisting only of ethylene with triethoxysilane is 3.8 ppm, an isomerized vinylene group A peak (D) of 2 protons is observed at 5.4 ppm. When hydrosilylation is not sufficient, the peak (E) for two protons of the unreacted vinyl group is observed at 4.8 to 5.1 ppm, and the peak (F) for one proton is observed at 5.6 to 5.8 ppm. The As for the raw material vinyl group-containing compound, the main chain methylene (G) for two protons was observed at 1.0 to 1.5 ppm, and the one having no vinyl group at the end of the main chain was terminal methyl (H ) Is observed at 0.8 ppm. Furthermore, the peak (I) for two protons on the carbon adjacent to the double bond is observed at 1.9 ppm.

  If the peak areas of each peak (C), (D), (E), (F), (G), (H) and (I) are respectively SC, SD, SE, SF, SG, SH and SI Yield (YLD (%)), conversion rate (CVS (%)), isomerization rate (ISO (%)), terminal unsaturation rate (VE (%)) are calculated by the following formulae.

YLD (%) = (SC / 3) / (SC / 3 + SD + SE) × 100
CVS (%) = {1-SE / (SC / 3 + SD + SE)} × 100
ISO (%) = SD / (SC / 3 + SD + SE) × 100
VE (%) = SE / (SE / 2 + SH / 3) × 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. under 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 was used.

(1) Rubber (α): Copolymer (A)
As the ethylene / α-olefin / non-conjugated polyene copolymer (A), Mitsui Chemicals, Inc. Mitsui EPT (registered trademark) 4045M (structural unit derived from ethylene: 45 wt%, structural unit derived from diene: 7.6% by weight, Mooney viscosity ML _{(1 + 4)} (100 ° C.) (ASTM D 1646): 45) was used.

(2) Rubber (α): Copolymer (B)
As the ethylene / α-olefin / non-conjugated polyene copolymer (B), Mitsui EPT (registered trademark) K9720 manufactured by Mitsui Chemicals, Inc. (structural unit derived from ethylene: 77 wt%, structural unit derived from diene) 10.4% by weight, Mooney viscosity ML _{(1 + 4)} (100 ° C.) (ASTM D 1646): 20) was used.

(3) Silylated polyolefin (β) (EXFORA)
[Synthesis Example 1]
(Synthesis of polyethylene having a vinyl group at one end)
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 3.89 g (15.0 mmol) of 3-cumyl-5-methylsalicylaldehyde, 30 ml of toluene and 2.54 g of ethylamine (40% aqueous solution, 22.5 mmol). Stir 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).

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

A stainless steel autoclave with an internal volume of 2000 ml sufficiently purged with nitrogen was charged with 1000 ml of heptane at room temperature, 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. MMAO (manufactured by Tosoh Finechem) 0.5 ml (0.5 mmol) of hexane solution (1.00 mmol / ml in terms of aluminum atoms) was injected, and then 0.5 ml of a toluene solution of compound B-1 (0.0002 mmol / ml) (0.0001 mmol) was injected to initiate the polymerization. After carrying out the polymerization at 150 ° C. for 30 minutes in an ethylene gas atmosphere, the polymerization was stopped by press-fitting a small amount of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours.

^{From the 1} H-NMR measurement, it was clear that the obtained polymer was homopolyethylene and contained a double bond only at one end. The physical properties of this one-terminal double bond-containing ethylene polymer (P-1) (single) were as follows.

Melting point (Tm) 123 ° C
Mw = 4770, Mw / Mn = 2.25 (GPC)
Terminal unsaturation 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 chloride (II) was added to hydrosilane A having the following structure (HS (A), manufactured by Momentive Performance Materials Japan GK, product number: XF40-C2195). (10 ml) and suspended 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 A 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 terminal vinyl group into hydrosilane-1)
A 300 ml two-necked flask was charged with 25.1 g (11.8 mmol) of the one-end vinyl group-containing ethylene polymer (P-1) obtained in [Synthesis Example 1], and hydrosilane A ( HS (A)) 8.7 g (5.9 mmol; equivalent to 11.8 mmol as Si—H group) and the platinum catalyst composition (C-1) prepared in [Synthesis Example 2] were hydrosilane A (HS (A)). ) (C-1a) 150 μl (1.4 × 10 ⁻⁶ mmol in terms of Pt) was charged. The reactor was set in an oil bath that had been heated to an internal temperature of 130 ° C. in advance, and stirred. After about 3 minutes the polymer melted. Then, after 6 hours, the mixture was cooled, about 200 ml of methanol was added, and the contents were taken out into a 300 ml beaker and stirred for 2 hours. Thereafter, the solid was collected by filtration, washed with methanol, and dried under reduced pressure at 60 ° C. and 2 hPa or less to obtain 33.1 g of a white solid silylated polyolefin (A-1). 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%. MFR was not less 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 mass%.

(4) Filler (C)
Silica VN3 GRType (primary particle size: 15 nm, secondary aggregate particle size: 18 μm, specific surface area: 200 m ² / g) manufactured by Tosoh Silica Co., Ltd. was used as the filler (C).

  In the present invention, each physical property was evaluated as follows.

(1) Hardness test The flat part of the vulcanized molded body was overlapped to 12 mm, and the hardness (durometer A hardness) was measured according to JIS K6253.

(2) Tensile test A vulcanized molded body was subjected to a tensile test in accordance with JIS K6251 under the conditions of a measurement temperature of 23 ° C and a tensile speed of 500 mm / min, and a modulus at 25% elongation (M25) and a modulus at 50% elongation (M50). ), Modulus at 100% elongation (M100), modulus at 200% elongation (M200), modulus at 300% elongation (M300), strength at break (TB), and elongation at break (EB).

(3) DIN friction test (DIN wear)
Using a 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 produced in accordance with JIS-K6264-2: 2005. Using a testing machine, a drum with a diameter of 150.0 ± 0.2 mm and a length of 500 mm was rotated at 40 times / min, and the wear amount when the load was 1 kgf and the wear distance was 40.0 ± 0.2 m ( DIN wear amount: unit mg) was measured.

(4) Crosslinking density After cutting a sheet-like sample into a size of 20 mm × 20 mm × 2 mmt, it was swollen by immersing in toluene at 37 ° C. for 72 hours according to JIS K 6258 (1993), and the Flory-Rehner formula (B) Thus, the effective network chain density (crosslinking density) was calculated.

Wherein (B) is a [nu (pieces / cm ³⁾ Effective network chain density (crosslinking density), the number of effective network chains of pure rubber 1cm in ^3, V _R is the net rubber crosslinked rubber swollen 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 from the vulcanized molded body to prepare a test piece. About this sample, the strain modulus dependence of the storage elastic modulus G 'was measured using the dynamic viscoelasticity testing machine. The measurement conditions are as follows.

Dynamic Viscoelasticity Tester (RDS): Rheometrics Sample: Used by punching a 2 mm sheet into a 25 mm diameter circle.

Temperature: 100 ° C
Distortion: 0.01% to 10%
Frequency: 10Hz
When the storage elastic modulus G ′ at the obtained strain rate of 0.01% is G ′ (0.01%) and the storage elastic modulus G ′ at the strain rate of 1.00% is G ′ (1.00%), the filler dispersion The sex index FDI (%) was calculated from the following formula (1).

FDI = G ′ (1.00%) / G ′ (0.01%) × 100 (1)
[Comparative Example 1]
MIXTRON BB MIXER (manufactured by Kobe Steel, Ltd., BB-4 type, volume 2.95 L, rotor 4WH) is used, with respect to 60 parts by weight of copolymer (A) and 40 parts by weight of copolymer (B), 80 parts by weight of silica (C), 1 part by weight of silicon (Si69, manufactured by Evonik) as a coupling agent, 1 part by weight of polyethylene glycol (PEG # 4000, manufactured by Sanyo Chemical Industries, Ltd.) as a surfactant, 5 parts by weight of zinc oxide (Zinc Hana, # 1, manufactured by Hakusuitec Co., Ltd.) as a vulcanization acceleration aid, 1 part by weight of stearic acid as a processing aid, and process oil (Diana Process Oil PS-430, Idemitsu Kosan Co., Ltd.) 15 parts by weight of the product) was kneaded to obtain a composition before vulcanization. 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 compound was 40 ° C., di-2-benzothiazolyl disulfide (MBTS, Ouchi Shinsei Chemical Industry) was used as a vulcanization accelerator in the compound using a 6-inch roll. 0.5 parts by weight), and 0.5 part by weight of vulcanization accelerator N-cyclohexyl-2-benzothiazolesulfenamide (CBS, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 1.0 parts by weight of tetramethylthiuram disulfide (TMTD, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1.0 part of zinc dibutyldithiocarbamate (ZnBDC, manufactured by Ouchi Shinsei Chemical Co., Ltd.) as a vulcanization accelerator. Part by weight and 1.0 part by weight of sulfur as a vulcanizing agent were kneaded. The kneading conditions were as follows: roll temperature: front roll / rear roll = 50 ° C./50° C., roll rotation speed: front roll / rear roll = 18 rpm / 15 rpm, roll gap of 5 mm, and kneading time 8 minutes.

  Next, this compound was vulcanized at 180 ° C. for 15 minutes using a press molding machine to prepare a rubber sheet (vulcanized molded body) having a thickness of 2 mm.

  The obtained vulcanized molded body was subjected to a hardness test, a tensile test, a DIN friction test, a crosslinking density, and a filler dispersion index by the above methods. The results are shown in Table 1.

[Example 1]
Comparative Example 1 is the same as Comparative Example 1 except that 1 part by weight of silylated polyolefin (β) (exfora) is added to 60 parts by weight of copolymer (A) and 40 parts by weight of copolymer (B). As well as. The results are shown in Table 1.

[Example 2]
Comparative Example 1 is the same as Comparative Example 1 except that 5 parts by weight of silylated polyolefin (β) (exformer) is added to 60 parts by weight of copolymer (A) and 40 parts by weight of copolymer (B). As well as. The results are shown in Table 1.

Example 3
Comparative Example 1 is the same as Comparative Example 1 except that 10 parts by weight of silylated polyolefin (β) (exfora) is added to 60 parts by weight of copolymer (A) and 40 parts by weight of copolymer (B). As well as. The results are shown in Table 1.

Claims (6)

A hulling roll having a rubber layer on the surface,
The rubber layer has a rubber component (α),
A silicon-containing compound containing a structural unit represented by the following formula (1) and a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) are 100 to 500 with respect to 100 parts by weight of the rubber component. Silylated polyolefin and / or a derivative thereof (β) which is a reaction product with a vinyl group-containing compound of 1,000,000 (however, the silicon-containing compound having two or more SiH groups per molecule as the silicon-containing compound, and 0.01 to 100 parts by weight in total of a silylated polyolefin, which is a reaction product with a vinyl group-containing compound having an average of 2.0 or more vinyl groups per molecule as a vinyl group-containing compound, and derivatives thereof ,
A hulling comprising a composition containing 1 to 100 parts by weight of filler (C) (excluding carbon black) satisfying the following requirement (C-1) with respect to 100 parts by weight of the rubber component roll.
-Si (R ¹ ) H-Y ^1- (1)
(In the 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).
(C-1) The average particle size is 10 μm to 50 μm. The rubber component (α) is an ethylene / α-olefin / nonconjugated polyene copolymer (A) satisfying the following requirements (A-1) and (A-2): 0 to 99 parts by weight, -1) and (B-2) containing 1 to 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene copolymer (B) (provided that the copolymer (A) and the copolymer (B ) Is 100 parts by weight)
The hulling roll according to claim 1.
(A-1) The structural unit derived from ethylene (E) is contained at 40 to 70% by weight.
(A-2) Mooney viscosity ML _{(1 + 4)} (100 ° C.) at 100 ° C. obtained by measurement according to ASTM D 1646 is 1-50.
(B-1) A structural unit derived from ethylene (E) is contained in an amount exceeding 70% by weight and 99% by weight or less.
(B-2) Mooney viscosity ML _{(1 + 4)} (100 ° C.) at 100 ° C. obtained by measurement according to ASTM D 1646 is ₁ to 90.   The hulling roll according to claim 1 or 2, wherein the composition further contains a crosslinking agent (D).   The hulling roll according to claim 3, wherein the crosslinking agent (D) is a vulcanizing agent, and the vulcanizing agent is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the rubber component.   The hulling roll as described in any one of Claims 1-4 whose durometer A hardness measured based on JISK6253 of this rubber layer is 10-100. It is a method for producing a hulling roll having a rubber layer on the surface,
The manufacturing method comprises:
100 parts by weight of rubber component (α),
A silicon-containing compound containing a structural unit represented by the following formula (1) and a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) are 100 to 500 with respect to 100 parts by weight of the rubber component. Silylated polyolefin and / or a derivative thereof (β) which is a reaction product with a vinyl group-containing compound of 1,000,000 (however, the silicon-containing compound having two or more SiH groups per molecule as the silicon-containing compound, and 0.01 to 100 parts by weight in total of a silylated polyolefin, which is a reaction product with a vinyl group-containing compound having an average of 2.0 or more vinyl groups per molecule as a vinyl group-containing compound, and derivatives thereof ,
A composition containing 1 to 100 parts by weight of filler (C) (excluding carbon black) satisfying the following requirement (C-1) with respect to 100 parts by weight of the rubber component is used as the crosslinking agent (D). A method for producing a hulling roll, comprising a step of crosslinking in the presence to obtain a rubber layer.
-Si (R ¹ ) H-Y ^1- (1)
(In the 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).
(C-1) The average particle size is 10 μm to 50 μm.