JP2022008084A - Molded bale of rubber composition, method for producing molded bale of rubber composition, crosslinking rubber composition, and tread for tire - Google Patents

Abstract

[Problem] To obtain a bale molded product of a rubber composition which is less likely to contaminate a molding die, is less likely to increase in viscosity over time, is less likely to peel off from the bale molded product, and allows a packaging sheet to easily adhere to the bale molded product. [Solution] To obtain a bale molded product of a rubber composition which contains a rubber-like polymer (A) having an iodine value of 10 to 250, an ethylene structure ≧3 mass%, and a vinyl aromatic monomer block <10 mass%, and titanium (C), the titanium (C) content being 3 ppm≦120 ppm, and the aluminum (B) content being less than 2 ppm. [Selected drawing] None

Description

The present invention relates to a veil-molded rubber composition, a method for producing a veil-molded rubber composition, a rubber composition for cross-linking, and a tread for a tire.

In recent years, in the field of rubber materials for tire treads, sheets, films, and asphalt reformers, rubber-like polymers having an ethylene structure and having crosslinkable unsaturated groups have been introduced for the purpose of increasing mechanical strength and compression set. A rubber composition containing the mixture has been proposed (see, for example, Patent Documents 1 to 3).

International Publication No. 2019/151126 International Publication No. 2019/151127 International Publication No. 2019/078083

However, in the rubber composition containing a rubber-like polymer having an ethylene structure and a crosslinkable unsaturated group, which has been conventionally proposed, the molding mold is easily contaminated and the rubber composition becomes viscous over time. It has a problem that it tends to rise easily and the rubber composition tends to be easily peeled off from the bale molded product. In addition, the present inventor has determined that a veil-molded rubber composition containing a rubber-like polymer having an ethylene structure is easily torn during transportation or the veil wrapped in the veil-molded product is easily torn during transportation. It has been found that the molded product has a problem that it tends to be difficult to carry. It is considered that this is because when the rubber-like polymer has an ethylene structure, it is difficult for the packaging sheet to adhere to the veil-molded body of the rubber composition.

Therefore, in the present invention, the molding die is less likely to be contaminated, the viscosity of the rubber composition is less likely to increase over time, the rubber composition is less likely to peel off from the veil molded body, and the packaging sheet is likely to adhere to the veil molded body. It is an object of the present invention to provide a veil molded product of a rubber composition.

As a result of diligent research and study in order to solve the above-mentioned problems of the prior art, the present inventors have determined the titanium content and the aluminum content in the rubber composition containing the rubber-like polymer having a specific structure. By specifying the range, the molding die is less likely to be contaminated, the rubber composition is less likely to increase in viscosity over time, the rubber composition is less likely to peel off from the veil molded body, and the packaging sheet is more likely to adhere to the bale molded body. We found that and came to complete the present invention.
That is, the present invention is as follows.

[1]
A rubber-like polymer (A) having an iodine value of 10 to 250, an ethylene structure of ≥3% by mass, and a vinyl aromatic monomer block <10% by mass.
Titanium (C) and
, Containing,
3 ppm ≤ titanium (C) content ≤ 120 ppm,
A veil molded product of a rubber composition having an aluminum (B) content of less than 2 ppm.
[2]
The veil molded product according to the above [1], wherein the rubber-like polymer (A) is a hydrogenated additive of a conjugated diene-based polymer.
[3]
The veil molded product according to the above [1] or [2], wherein the rubber-like polymer (A) contains 5% by mass or more of vinyl aromatic monomer units.
[4]
The veil molded product according to any one of the above [1] to [3], wherein the rubber-like polymer (A) contains a nitrogen atom.
[5]
The veil molded product according to any one of [1] to [4] above, wherein the modification rate of the rubber-like polymer (A) measured by the column adsorption GPC method is 40% by mass or more.
[6]
The veil molded product according to any one of the above [1] to [5], further containing 30% by mass or less of the softening agent (D) for rubber.
[7]
The veil molded product according to any one of the above [1] to [6], which contains 0.05% by mass or more and 1.5% by mass or less of water.
[8]
The method for producing a veil-molded rubber composition according to any one of [1] to [7] above.
A step of polymerizing at least a conjugated diene monomer in a solution to obtain a rubbery polymer (A), and
A step of adding titanium (C) to the obtained solution containing the rubber-like polymer (A) to obtain a rubber composition, and
The process of molding the obtained rubber composition and
A method for producing a veil-molded rubber composition.
[9]
The method for producing a veil molded product according to the above [8], wherein the hydrogenation step is performed using a hydrogenation catalyst having an aluminum content of 0.05 mol or less with respect to 1 mol of titanium content.
[10]
The method for producing a veil molded product according to the above [8] or [9], which comprises a step of removing the solvent from the solution by steam stripping.
[11]
The rubber composition of the veil molded product according to any one of [1] to [7] above, and the rubber composition.
With a cross-linking agent,
, Containing,
A rubber composition for cross-linking containing the cross-linking agent in an amount of 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component.
[12]
A tread for a tire containing the rubber composition of the veil molded product according to any one of the above [1] to [7].

According to the present invention, the molding die is less likely to be contaminated, the viscosity of the rubber composition is less likely to increase over time, the rubber composition is less likely to peel off from the veil molded body, and the packaging sheet is more likely to adhere to the veil molded body. You get things.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following embodiments. The present invention can be appropriately modified and carried out within the scope of the gist thereof.

[Veil molded product of rubber composition]
The veiled product of the rubber composition of the present embodiment is a rubber-like polymer having an iodine value of 10 to 250, an ethylene structure of ≧ 3% by mass, and a vinyl aromatic monomer block <10% by mass. A veil-molded rubber composition containing (A) and titanium (C), with a content of 3 ppm ≤ titanium (C) ≤ 120 ppm and a content of aluminum (B) of less than 2 ppm.

(Rubber-like polymer (A))
The rubber-like polymer (A) contained in the rubber composition constituting the veil molded product of the present embodiment (hereinafter, referred to as the rubber composition of the present embodiment) has an iodine value of 10 to 250 and is ethylene. It is a rubber-like polymer having a structure of ≧ 3% by mass and a vinyl aromatic monomer block <10% by mass.

<Iodine value>
The iodine value of the rubber-like polymer (A) constituting the rubber composition of the present embodiment is 10 to 250.
The iodine value is 10 or more from the viewpoint of ease of crosslinking and the adhesion of the packaging sheet of the veil molded product of the rubber composition of the present embodiment. 15 or more is preferable, 30 or more is more preferable, 50 or more is further preferable, and 70 or more is even more preferable.
On the other hand, it is 250 or less from the viewpoint of weather resistance and aging resistance of the rubber-like polymer (A), mechanical strength and wear resistance when made into a tire. 170 or less is preferable, 140 or less is more preferable, 110 or less is further preferable, and 80 or less is even more preferable.
The iodine value can be measured according to the method described in "JIS K 0070: 1992".
Since the iodine value is a value representing the amount of halogen that reacts with 100 g of the target substance in terms of the number of grams of iodine, the unit of iodine value is "g / 100 g".
Since the conjugated diene monomer unit has a double bond, for example, in the method for producing the rubbery polymer (A) described later, for example, the conjugated diene monomer and the vinyl aromatic monomer are copolymerized. In this case, the lower the content of the conjugated diene monomer unit, the lower the iodine value of the rubber-like polymer (A), and when the conjugated diene monomer unit is hydrogenated, the hydrogenation rate is high. The iodine value is lower.
The iodine value of the rubbery polymer (A) includes the amount of conjugated diene monomer having an unsaturated bond added, the polymerization time, the polymerization conditions such as the polymerization temperature, the amount of hydrogenation in the hydrogenation step, the hydrogenation time, etc. By adjusting the conditions, it can be controlled within the above numerical range.

<Content of ethylene structure>
The rubber-like polymer (A) constituting the rubber composition of the present embodiment has an ethylene structure of 3% by mass or more.
When the ethylene structure is 3% by mass or more, it is easy to exhibit the fracture characteristics required for rubber for tires. The ethylene structure is preferably 5% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more.
The ethylene structure is preferably 90% by mass or less. 80% by mass or less is more preferable, and 70% by mass or less is further preferable.
When the ethylene structure is 90% by mass or less, the rubber composition of the present embodiment has excellent rubber elasticity.
The ethylene structure in the rubber-like polymer (A) includes all of an ethylene structure obtained by copolymerizing an ethylene monomer, an ethylene structure obtained by hydrogenating a conjugated diene monomer after polymerization, and the like. .. For example, when 1,4-butadiene units are hydrogenated, two ethylene structures are obtained, and when 1,4-isoprene units are hydrogenated, one propylene structure and one ethylene structure are obtained.
The content of the ethylene structure of the rubber-like polymer (A) can be measured by the method described in Examples described later, and the amount of ethylene added, the amount of conjugated diene monomer added, the hydrogenation rate and the like are adjusted. By doing so, it is possible to control within the above numerical range.

<Vinyl aromatic monomer block content>
The rubber-like polymer (A) has a vinyl aromatic monomer block content of less than 10% by mass (vinyl aromatic monomer block <10% by mass).
The vinyl aromatic monomer block means a block in which eight or more vinyl aromatic monomer units are chained.
When the content of the vinyl aromatic monomer block is less than 10% by mass, the rubber composition of the present embodiment tends to show good peel resistance, and the formability of the rubber composition into a veil-molded body and the veil-molded body are improved. Has excellent cutability during weighing. The content of the vinyl aromatic monomer block is preferably 7% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
The vinyl aromatic monomer block has a small number or no blocks in which 30 or more vinyl aromatic monomer units are chained from the viewpoint of flexibility of the rubber-like polymer or the rubber composition. Is preferable.
Specifically, when the polymer constituting the rubber-like polymer (A) is a butadiene-styrene copolymer, the content of the vinyl aromatic monomer block is determined by the method of Koltoff (IM KOLTHOFF, et.). It can be measured by decomposing the polymer by the method described in al., J. Polym. Sci. 1,429 (1946) and analyzing the amount of polystyrene insoluble in methanol. As another method, as described in International Publication No. 2014-13309, measurement can be performed by a known method such as measuring the chain of styrene units using NMR.
The vinyl aromatic monomer block content of the rubber-like polymer (A) is controlled within the above numerical range by adjusting the method of adding the vinyl aromatic monomer, the addition of the polymerization aid, the polymerization temperature, and the like. be able to.

<Monomer unit in which an unsaturated group is contained in the rubber-like polymer (A)>
The rubber-like polymer (A) preferably contains 2% by mass or more of a conjugated diene monomer unit or a monomer unit having an unsaturated group such as myrcene. From the viewpoint of economy and manufacturability, it is more preferable to contain the conjugated diene monomer unit.
Since the conjugated diene monomer unit and myrcene contained as a component of the rubber-like polymer (A) have a double bond, they become crosslinkable unsaturated groups.
The content of the conjugated diene monomer unit or the monomer unit having an unsaturated group such as myrcene in the rubber-like polymer (A) is closely related to the iodine value described above.
When the content of the conjugated diene monomer unit or the monomer unit having an unsaturated group such as myrcene is 2% by mass or more, it is easy to crosslink and the rubber composition is adhered to the packaging sheet of the veil molded body. It will be excellent in terms of sex. The content of the conjugated diene monomer unit is more preferably 3% by mass or more, still more preferably 6% by mass or more.
The content of the conjugated diene monomer unit or the monomer unit having an unsaturated group such as myrcene is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less. In this case, the mechanical strength and wear resistance when made into a tire are excellent.
The content of the conjugated diene monomer unit of the rubber-like polymer (A) or the monomer unit having an unsaturated group such as myrcene can be measured by the method described in Examples described later, and hydrogen described later. By adjusting the addition rate, it can be controlled within the above numerical range.

(Aluminum (B))
The rubber composition of the present embodiment has an aluminum (B) content of less than 2 ppm. Within this range, the rubber composition of the present embodiment exerts an effect of suppressing an increase in viscosity with time.
The reason why the rubber composition of the present embodiment can be prevented from increasing in viscosity with time by suppressing the concentration of aluminum (B) to be low is that the rubber composition contains an aluminum content of 2 ppm or more. It is considered that the aluminum-containing compound is dispersed in the form of fine particles and the heteroatom of the rubber-like polymer and the residue of the coupling agent interact with each other to increase the viscosity. Therefore, when the content of aluminum is less than 2 ppm, such an increase in viscosity can be suppressed.
In particular, the rubber-like polymer (A) described later has a weight average molecular weight of 310,000 or more, contains a nitrogen atom, and the nitrogen atom easily becomes a primary amine, and further, a coupling having an alkoxysilane. When the agent is contained, the effect of suppressing the increase in viscosity with time is remarkable when the aluminum content is less than 2 ppm.
The content of aluminum (B) is the amount of each element even if it is contained as a compound containing aluminum.
The aluminum content of the rubber-like polymer (A) can be measured by the method described in Examples described later, and the type and amount of the polymerization catalyst and hydrogenation catalyst added, decalcification, or removal of the solvent described later. By adjusting the conditions of the process, it is possible to control within the above numerical range.

(Titanium (C))
The content of titanium (C) in the rubber composition of the present embodiment is 3 ppm or more and 120 ppm or less (3 ppm ≤ titanium (C) content ≤ 120 ppm).
From the viewpoint of stain resistance of the molding die at the time of molding the rubber composition, it is 3 ppm or more, more preferably 10 ppm or more, still more preferably 15 ppm or more.
On the other hand, from the viewpoints of difficulty in peeling the rubber composition from the bale molded product, difficulty in clogging the mesh due to the gel component when the viscosity of the rubber composition increases over time, and adhesion of the packaging sheet to the veil molded product. , 120 ppm or less. 100 ppm or less is more preferable, 50 ppm or less is further preferable, and 30 ppm or less is even more preferable.
The reason why the presence of titanium (C) can suppress the contamination of the molding mold is that the presence of metal particles on the contact surface with the mold, like the effect of baby powder, causes the polymer to adhere to the mold. Is thought to be alleviated.
The content of titanium (C) can be controlled within the above numerical range by adjusting the amount of the hydrogenation catalyst containing titanium, which will be described later, the step of removing the solvent from the polymerization solvent, and the like.

(Preferable structure of rubber-like polymer (A))
<Hydrogenated polymer>
The rubber-like polymer (A) is a part or most of the double bonds in the rubber-like polymer obtained by polymerizing or copolymerizing at least a conjugated diene monomer unit or a monomer unit having an unsaturated group such as Milsen. It is preferable that the polymer is a hydrogenated polymer obtained by hydrogenating (hydrogenating) the above.
The unsaturated group in the rubbery polymer (A) contains an unsaturated group derived from a conjugated diene monomer unit or a monomer such as myrcene. That is, in the production process of the rubbery polymer (A), at least one of the double bonds in the polymer after polymerizing or copolymerizing at least a conjugated diene monomer unit or a monomer unit having an unsaturated group such as Milsen. When hydrogenating (hydrogenating) a part or most of the conjugated diene monomer unit, the conjugated diene monomer unit left without hydrogenation so as to have a predetermined iodine value is included. Is preferable.

<Monomer constituting the rubber-like polymer (A)>
The rubbery polymer (A) can be formed of a conjugated diene monomer and, if necessary, other monomers.
The conjugated diene monomer is not limited to the following, but is, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-. Included are 1,3-pentadiene, 1,3-hexadiene, and 1,3-heptadiene. Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable from the viewpoint of easy industrial availability. These may be used alone or in combination of two or more.
The monomer used as needed is not particularly limited, but it is preferable to copolymerize the vinyl aromatic monomer from the viewpoint of mechanical strength when the tire is made. The vinyl aromatic monomer is not limited to the following, and is, for example, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene, vinylbenzyldimethylamine, and the like. (4-Vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, N, N-dimethylaminomethylstyrene, tertiary amino group-containing diphenylethylene (eg, 1- (4-N, N-dimethylamino) Styrene) -1-phenylethylene) and the like can be mentioned. Among these, styrene is preferable from the viewpoint of easy industrial availability.
These may be used alone or in combination of two or more.
The following monomers can also be used as other monomers used as needed.
For example, unsaturated carboxylic acid ester, unsaturated carboxylic acid, α, β-unsaturated nitrile compound, α-olefin (butylene, propylene, butylene, pentene, hexene, etc.), ethylene, milsen, etilidennorbornene, isopropyridennorbornene, cyclo. Examples thereof include pentadiene and divinylbenzene.

<Amount of vinyl bond of rubber-like polymer (A)>
For the rubber-like polymer (A), the vinyl bond amount of the conjugated diene monomer unit of the conjugated diene-based polymer before hydrogenation is important, and the vinyl bond amount in the conjugated diene monomer unit is the rubber-like weight. From the viewpoint of the productivity of the coalescence (A) and the high wet skid resistance when made into a tire, 10 mol% or more is preferable, and 20 mol% or more is more preferable. Further, from the viewpoint of mechanical strength when used in a tire, 75 mol% or less is preferable, 60 mol% or less is more preferable, 45 mol% or less is further preferable, and 30 mol% or less is even more preferable.
The vinyl bond amount can be measured by the method described in Examples described later.
The vinyl bond amount can be controlled within the above numerical range by adjusting the polymerization temperature and the amount of the polar compound added to the polymerization.

<Polymerization and hydrogenation steps of the rubber-like polymer (A)>
The polymerization step and the hydrogenation step for producing the rubber-like polymer (A) may be either a batch type or a continuous type, respectively.
The intramolecular or intramolecular distribution of the hydrogenation rate, ethylene, conjugated diene monomer, vinyl aromatic monomer and other monomers in the rubbery polymer (A) is not particularly limited and may be uniform. , It may be non-uniform or may have a distribution.

<Contents of vinyl aromatic monomer unit>
The content of the vinyl aromatic monomer unit in the rubber-like polymer (A) is determined from the viewpoint of deformation resistance during transportation of the molded product, fracture strength when used for a tire tread, and wet skid resistance. 5% by mass or more is preferable, 10% by mass or more is more preferable, 15% by mass or more is further preferable, and 20% by mass or more is even more preferable.
On the other hand, 45% by mass or less is preferable, 30% by mass or less is more preferable, and 25% by mass or less is preferable from the viewpoint of cutability at the time of weighing the bale molded body, fuel efficiency and wear resistance when used for a tire tread. Is even more preferable.
Further, when high modulus such as a run-flat tire member is required, 30% by mass or more is preferable.
The content of the vinyl aromatic monomer unit of the rubber-like polymer (A) can be measured by the method described in Examples described later, and by adjusting the addition amount of the vinyl aromatic monomer in the polymerization step, It can be controlled within the above numerical range.

<Nitrogen atom>
The rubber-like polymer (A) preferably contains nitrogen atoms from the viewpoint of peeling resistance of the rubber composition from the molded product of the rubber composition and fuel efficiency when the rubber composition is used as a tire.
The nitrogen atom can be contained in the rubber-like polymer (A) in the production step of the rubber-like polymer (A), for example, by using a coupling agent containing a nitrogen atom.

<Denaturation rate>
The rubber-like polymer (A) has a modification rate of 40% by mass measured by the column adsorption GPC method of the rubber-like polymer (A) from the viewpoint of the dispersibility of silica when manufactured into a tire using silica. The above is preferable, 60% by mass or more is more preferable, and 70% by mass or more is further preferable.
In the present specification, the "modification rate" represents the mass ratio of the polymer having a nitrogen atom-containing functional group to the total amount of the rubber-like polymer (A).
The position of introducing the nitrogen atom into the rubber-like polymer (A) may be any of the polymerization initiation end, the molecular chain (including the graft product), and the polymerization end of the rubber-like polymer (A). ..

The rubber-like polymer (A) is made of nitrogen or tin by using a coupling agent containing a tin atom or a nitrogen atom from the viewpoints of polymerization productivity, high modification rate, wear resistance and fuel saving when made into a tire. It is preferable to introduce atoms into the rubbery polymer (A). It is more preferable to introduce the nitrogen atom into the rubber-like polymer (A) by using a coupling agent containing a nitrogen atom.

Coupling agents containing a nitrogen atom include an isocyanato compound, an isothiocyanate compound, an isocyanuric acid derivative, a nitrogen group-containing carbonyl compound, a nitrogen group-containing vinyl compound, and a nitrogen group from the viewpoint of polymerization productivity and high modification rate. Epoxy compounds, nitrogen group-containing alkoxysilane compounds and the like are preferable.
As the coupling agent containing these nitrogen atoms, a nitrogen group-containing alkoxysilane compound is more preferable from the viewpoint of the polymerization productivity of the rubber-like polymer (A), the high modification rate, and the tensile strength when the tire is made.

The nitrogen group-containing alkoxysilane compound is not limited to the following, and is, for example, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2, 2-Diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane , 2,2-Dimethoxy-1- (5-trimethoxysilylpentyl) -1-aza-2-silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza-2 -Silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-trimethoxysilylpropyl) ) -1-aza-2-silacyclopentane, 2-ethoxy,2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1 -(3-Dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, and 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane , Tris (3-trimethoxysilylpropyl) amine, Tris (3-methyldimethoxysilylpropyl) amine, Tris (3-triethoxysilylpropyl) amine, Tris (3-methyldiethoxysilylpropyl) amine, Tris (trimethoxy) Cyrilmethyl) amine, tris (2-trimethoxysilylethyl) amine, and tris (4-trimethoxysilylbutyl) amine, tetrakis [3- (2,2-dimethoxy-1-aza-2-silacyclopentane) propyl ] -1,3-Propyldiamine, Tetrax (3-trimethoxysilylpropyl) -1,3-Propyldiamine, Tetrax (3-trimethoxysilylpropyl) -1,3 ^- bisaminomethylcyclohexane, and N1-( 3- (Bis (3- (trimethoxysilyl) propyl) amino) propyl) -N ¹ -methyl-N ^3- (3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl) -N ^3- (3- (Trimethoxysilyl) propyl) -1,3-propanediamine can be mentioned.

(Rubber-like polymer (A), physical properties of rubber composition)
<Glass transition temperature>
The glass transition temperature of the rubber-like polymer (A) is preferably −90 ° C. or higher, more preferably −80 ° C. or higher, still more preferably −75 ° C. or higher, from the viewpoint of tensile strength when made into a tire.
On the other hand, from the viewpoint of the cutting resistance of the sheet at the time of manufacturing the tire and the flexibility at the time of making the tire, the temperature is preferably −15 ° C. or lower, more preferably −30 ° C. or lower, still more preferably −40 ° C. or lower.
Regarding the glass transition temperature, according to ISO 22768: 2006, the DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Infection point) of the DSC differential curve is defined as the glass transition temperature.

<Weight average molecular weight>
The weight average molecular weight of the rubber-like polymer (A) is the shape stability of the molded product using the rubber composition of the present embodiment, and the tensile strength, wear resistance, and crack resistance of the crosslinked product using the rubber composition. From the viewpoint of the above, 150,000 or more is preferable, 200,000 or more is more preferable, 310,000 or more is further preferable, and 350,000 or more is even more preferable.
On the other hand, from the viewpoint of processability when the rubber composition of the present embodiment is made into a rubber composition for crosslinking, 1 million or less is preferable, 500,000 or less is more preferable, and 400,000 or less is further preferable.
The molecular weight distribution (= weight average molecular weight / number average molecular weight) of the rubber-like polymer (A) is preferably 2.0 or less, preferably 1.8 or less, from the viewpoint of fuel efficiency when the rubber composition is used for a tire. Is more preferable, and 1.6 or less is further preferable.
On the other hand, from the viewpoint of processability when the rubber composition is made into a cross-linking rubber composition, 1.05 or more is preferable, 1.2 or more is more preferable, and 1.4 or more is further preferable.
The weight average molecular weight and the molecular weight distribution can be calculated from the polystyrene-equivalent molecular weight measured by GC (gel permeation chromatography), and can be measured by the method described in Examples described later.

<Moony viscosity>
The Mooney viscosity of the rubber-like polymer (A) and the rubber composition of the present embodiment is an index including information such as the molecular weight, the molecular weight distribution, the degree of branching, and the content of the softener of the rubber-like polymer (A). ..
The Mooney viscosity of the rubber composition of the present embodiment measured at 100 ° C. is preferably 40 or more, preferably 50 or more, from the viewpoint of wear resistance, steering stability, and breaking strength when the rubber composition for crosslinking is used for a tire. The above is more preferable, and 55 or more is further preferable.
On the other hand, 170 or less is preferable, and 150 or less is more preferable, from the viewpoint of productivity of the rubber-like polymer (A) and the rubber composition of the present embodiment, and processability when a composition containing a filler or the like is prepared. 130 or less is more preferable. 110 or less is even more preferable.
As the method for measuring Mooney viscosity, the method specified in ISO289 can be applied.

(Rubber softener (D))
The rubber composition of the present embodiment may contain a rubber softening agent (D), if necessary. The rubber softening agent (D) is preferably 30% by mass or less.
In the rubber composition of the present embodiment, the softener for rubber (D) is added in order to improve the productivity of the rubber-like polymer (A) and the processability when an inorganic filler or the like is blended during tire production. The amount is preferably 1 to 30% by mass.
When the molecular weight of the rubber-like polymer (A) is high, for example, when the weight average molecular weight exceeds 1 million, the amount of the rubber softener (D) added is preferably 15 to 30% by mass, while the filler. In the case of a rubber composition containing the above, the amount of the softening agent for rubber (D) added is preferably 1 to 15% by mass from the viewpoint of increasing the degree of freedom of blending.
The content of the softening agent (D) for rubber in the rubber composition of the present embodiment is 20% by mass or less from the viewpoint of suppressing deterioration over time when the tire is made and from the viewpoint of stain resistance of the molding die. It is preferable, 10% by mass or less is more preferable, and 5% by mass or less is even more preferable.

The softening agent (D) for rubber is not particularly limited, and examples thereof include wrought oil, liquid rubber, and resin.
As the softening agent (D) for rubber, wrought oil is preferable from the viewpoint of processability, productivity and economy.
The method for adding the rubber softening agent (D) to the rubber composition of the present embodiment is not limited to the following, but the rubber softening agent is added to the polymer solution and mixed to contain the rubber softening agent. A method of desolving the polymer solution of the above is preferable.

Preferred spreading oils include, but are not limited to, aroma oils, naphthenic oils, paraffin oils and the like.
Among these, from the viewpoint of environmental safety, prevention of oil bleeding, and wet grip characteristics, an aroma substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less according to the IP346 method is preferable. Examples of the aroma substitute oil include TDAE (Treated Distillate Aromatic Extracts) shown in Kautschuk Gummy Kunststoffe 52 (12) 799 (1999), MES (Mild Extraction Extract), and RA.

[Method for manufacturing veil molded product of rubber composition]
The method for producing a veil-molded rubber composition of the present embodiment includes a step of polymerizing at least a conjugated diene monomer in a solution to obtain a rubber-like polymer (A) and a obtained rubber-like polymer (A). ) To a solution containing titanium (C) to obtain a rubber composition, and a step of molding the rubber composition.
The polymerization step is a polymerization step of a conjugated diene and / or a copolymerization step of a conjugated diene and an aromatic vinyl, and a compound containing titanium (C) functions as a hydrogenation catalyst in a solution containing a (co) polymer. By doing so, it is one of the preferable embodiments that the rubber-like polymer (A) is produced.

(Polymerization method of rubber-like polymer (A) and hydrogenation method)
The rubber-like polymer (A) is obtained by polymerizing at least a conjugated diene monomer or the conjugated diene thereof from the viewpoint of the production cost of the rubber-like polymer (A), fuel saving when used in a tire, and flexibility. Obtained by copolymerizing a monomer with another monomer.
It is preferable to hydrogenate (hydrogenate) a part or most of the double bonds in the rubber-like polymer (A).
The unsaturated group in the rubbery polymer (A) may include a conjugated diene monomer unit left without hydrogenation so as to have a predetermined iodine value among the conjugated diene monomer units. preferable.

As a method of polymerizing or copolymerizing at least a conjugated diene monomer and then hydrogenating, for example, International Publication No. 96/05250, JP-A-2000-053706, International Publication No. 2003/08010, International Publication No. 96/05250 As described in Japanese Patent Publication No. 2019/151126, International Publication No. 2019/151127, International Publication No. 2002/002663, and International Publication No. 2015/006179, under various additives and conditions. It is preferable to apply a method of polymerizing a conjugated diene monomer by anionic polymerization, copolymerizing with other monomers if necessary, and then hydrogenating.

(Titanium (C) in rubber composition)
The titanium (C) in the rubber composition of the present embodiment is preferably a catalyst residue at the time of producing the rubber-like polymer (A).
In such a case, titanium (C) as a catalyst is preferably a hydrogenation catalyst component.
As the hydrogenation catalyst component used in the production of the rubber-like polymer (A), for example, Japanese Patent Application Laid-Open No. 1-275605 from the viewpoint that the amount of metal in the rubber composition of the present embodiment can be easily adjusted to a predetermined amount. , Japanese Patent Laid-Open No. 2-172537, Japanese Patent Application Laid-Open No. 4-96904, Japanese Patent Application Laid-Open No. 08-33846, Japanese Patent Application Laid-Open No. 08-41081, International Publication No. 2014-046016, International Publication No. 2014-04017 , International Publication No. 2014-065283, International Publication No. 2017-090714, and International Publication No. 2017-090714 are preferred.
As the hydrogenation catalyst component, a mixture of a Ti compound and a Li compound and / or an Mg compound, or a reaction product is more preferable. From the viewpoint of hydrogenation rate, a mixture of Ti compound and Li compound, or a reaction product is more preferable.

Examples of the Ti compound include titanocene of the following formula (1).

(In the above formula (1), R ₁ and R ₂ represent a group selected from the group consisting of a hydrocarbon group of C1 to C12, an aryloxy group, an alkoxyl group, a halogen group, and a carbonyl group, and R ₁ ,. R ₂ may be the same or different.)

The Ti compound is not limited to the following from the viewpoint of high hydrogenation rate, but for example, bis (η5-cyclopentadienyl) titanium di (p-tolyl), bis (η5-cyclopentadi). Enyl) Titanium Di (Phenyl), Bis (η5-Cyclopentadienyl) Titanium Di (3,4-Kycyril), Bis (η5-Cyclopentadienyl) Titanium (Fluryloxy) Chloride, Bis (η5-Cyclopenta) Dienyl) Titanium dichloride is preferred.
From the economical point of view, bis (η5-cyclopentadienyl) titanium dichloride is more preferable.

The Li compound is not limited to the following, and for example, methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, isobutyl lithium, t-butyl lithium, and the like. n-pentyllithium, n-hexyllithium, phenyllithium, cyclopentadienyllithium, m-tolyllithium, p-tolyllithium, xylyllithium, dimethylaminolithium, diethylaminolithium, methoxylithium, ethoxylithium, n-propoxylithium , Isopropoxylithium, n-butoxylithium, sec-butoxylithium, t-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, benzyloxylithium, and Examples include 4-methylbenzyloxylithium.

The Mg compound is not limited to, but is not limited to, for example, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, ethylbutylmagnesium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, phenylmagnesium bromide, and the like. Examples include phenylmagnesium chloride, t-butylmagnesium chloride, and t-butylmagnesium bromide.

(Amount of titanium and aluminum in the polymer manufacturing process)
The amount of titanium (C) added as a hydrogenation catalyst component during the production of the rubber-like polymer (A) is preferably 150 ppm or less with respect to the polymer before hydrogenation. Within this range, it becomes easy to control the content of titanium (C) contained in the rubber composition of the present embodiment in the range of 3 ppm or more and 200 ppm or less.
The amount of aluminum (B) added during the production of the rubber-like polymer (A) is preferably 6 ppm or less. Within this range, it becomes easy to control the content of aluminum (B) contained in the rubber composition of the present embodiment to less than 2 ppm. Substantially, it is more preferable not to add aluminum from the viewpoint of reducing the aluminum (B) residue in the rubber composition of the present embodiment. Further, by using lithium or magnesium instead of aluminum, the function of aluminum as a co-catalyst can be complemented.
Further, from the viewpoint of suppressing the increase in Mooney viscosity (ML viscosity) and handling and safety of the hydrogen addition catalyst, the hydrogenation catalyst added at the time of producing the rubbery polymer (A) is based on 1 mol of titanium (C). , Aluminum (B) preferably has a content of 0.05 mol or less, more preferably aluminum (B) has a content of 0.04 mol or less, and aluminum (B) has a content of 0.03 mol or less. It is even more preferable that the content is, and it is even more preferable that the content of aluminum (B) is not contained.

(Amount of metal other than Al and Ti in the rubber composition)
As a metal other than aluminum (B) and titanium (C), the content of lithium in the rubber composition of the present embodiment is preferably 60 ppm or less from the viewpoint of color change resistance of the rubber composition of the present embodiment. 50 ppm or less is more preferable, 40 ppm or less is further preferable, and 30 ppm or less is even more preferable. On the other hand, from the viewpoint of tensile elongation at the time of cross-linking, 2 ppm or more is preferable, 5 ppm or more is more preferable, and 10 ppm or more is further preferable.

The content of titanium (C) and lithium described above is the amount of each element even if it is contained as a compound.

Further, when the titanium (C) in the rubber composition of the present embodiment is a residue of the hydrogenation catalyst component or the polymerization catalyst component, the titanium (C) is finely dispersed in the rubber composition and can be specified. It becomes a difficult compound or complex and may have a great influence on the physical properties of the rubber composition. Therefore, in the rubber composition of the present embodiment, from the viewpoint of not affecting the physical properties of the rubber composition, preventing the characteristics from becoming difficult, and further relaxing the adhesion of the rubber composition to the mold. It is preferable that titanium (C) is dispersed in the form of particles.

(Addition of additives)
In the production of the rubber composition of the present embodiment, after the polymerization step of the rubber-like polymer (A), the amount of metal in the rubber composition of the present embodiment is easily adjusted to a predetermined range. It is preferable to add a working agent, a neutralizing agent and the like.
The deactivating agent is not limited to the following, and examples thereof include water; alcohols such as methanol, ethanol, and isopropanol.
The neutralizing agent is not limited to the following, but is, for example, a carboxylic acid such as stearic acid, oleic acid, and versatic acid (a carboxylic acid mixture having 9 to 11 carbon atoms and mainly 10 branches). Acid: An aqueous solution of an inorganic acid, carbonic acid gas, and the like.
After the polymerization step of the rubber-like polymer (A), it is preferable to add a rubber stabilizer from the viewpoint of preventing gel formation and processing stability.
The stabilizer for rubber is not limited to the following, and known ones can be used, and for example, 2,6-di-tert-butyl-4-hydroxytoluene (hereinafter, also referred to as “BHT”). , N-Octadecyl-3- (4'-hydroxy-3', 5'-di-tert-butylphenol) propinate, 2-methyl-4,6-bis [(octylthio) methyl] phenol and other antioxidants are preferred. It is mentioned as a thing.

Various additives can be further added to the rubber composition of the present embodiment, if necessary. As such an additive, the filler shown below, a resin component as a tack fire, or the like can be added as a master batch in the step before molding. In that case, the additive is preferably 15% by mass or less.
The rubber composition of the present embodiment is a rubber-like polymer (A) + from the viewpoint of improving the balance between the handleability and mechanical strength of the rubber composition, the fuel saving property when used in a tire, and the wear resistance. The content of aluminum (B) + titanium (C) + rubber softener (D) is preferably 85% by mass or more, more preferably 95% by mass or more, and 97% by mass or more. Is even more preferable.

When producing the rubber composition of the present embodiment, the solvent is removed from the polymer solution after the step of polymerizing the rubber-like polymer (A) in the solution.
Examples of the method for removing the solvent from the polymer solution include a method using flushing, steam stripping, a drying conveyor after dehydration, a devolatilization extruder, a drum dryer, a devolatilization kneader and the like.
From the viewpoint that the heat history is small and the amount of metal in the rubber composition can be easily adjusted to a desired amount, at least a method using steam stripping is preferable. In particular, since it is difficult to adjust the metal amount of the rubber-like polymer (A) using a coupling agent containing a nitrogen atom, the method using steam stripping is useful from the viewpoint of adjusting the metal amount.
The steam stripping and the processing method before and after the steam stripping are not limited to the following, and are, for example, JP-A-10-168101, JP-A-10-204136, International Publication No. 2013-146530, JP-A. Examples thereof include the methods described in JP-A-2019-131810.

In the method for producing a rubber composition of the present embodiment, as a step before carrying out the extrusion drying step, a desolvation step of removing the solvent from the polymer solution by steam stripping and separation from the stripping water from the polymer slurry are performed. Therefore, it is preferable to carry out a screening step for removing the hydrous crumb.
Further, as a preliminary step of steam stripping, a flushing step may be provided in order to increase the solution concentration.
By carrying out a desolvation step of removing the solvent from the polymer solution by steam stripping as a pre-step before carrying out the extrusion drying step, a porous granular crumb containing no solvent and containing water is formed in hot water. A slurry dispersed in is obtained.
By carrying out a screening step of separating from the stripping water from the slurry of the polymer and taking out the hydrous crumb, a porous granular crumb containing water can be obtained.
Further, if necessary, it is preferable to carry out a squeezing dehydration step of dehydrating with a roll, a screw compression squeezing machine or the like. By these dehydration steps, it is possible to obtain a water-containing crumb with a lower water content before the extrusion-drying step.

As a method of controlling the content of titanium (C) in the rubber composition of the present embodiment by steam stripping to 3 ppm or more and 120 ppm or less, a solution of the rubber-like polymer (A) after polymerization and hot water or As conditions for contact with steam, a method of adjusting the solution injection pressure, a method of adjusting the pressure, temperature and amount of steam, a dispersant such as a phosphate ester such as polyoxyalkylene alkyl ether phosphate or a salt thereof, and the like, , A method of adding a surfactant such as nonylphenoxy polyethylene glycol phosphate ester or a salt thereof, a method of adjusting the shape and rotation speed of the rotary blade used for mixing, and the like are useful methods.

In the production of the rubber composition of the present embodiment, it is preferable to contain an alcohol compound as a deactivating agent in the polymer solution for economic efficiency and metal removal property, and further, it is added at the time of steam stripping. It is more preferable to add a dispersant or a surfactant in advance.

As a method for reducing the titanium (C) content in the rubber composition of the present embodiment, for example, an alcohol compound is added as a deactivating agent to the polymer solution after the polymerization of the rubber-like polymer (A). A method of adding 0.5 times or more, preferably 1.0 times or more, of the number of moles of the polymer (A), the volume ratio of the steam / polymer solution is 0.1 or more, preferably 0 in the steam stripping step. Examples thereof include a method of setting the content to 2 or more, a method of lowering the treatment rate, and a method of adding 100 ppm or more, preferably 200 ppm of a surfactant to the polymer in the polymer solution.

The rotary blade in the steam stripping step preferably has a linear speed of 5 m / s or more and 20 m / s or less, and more preferably a linear speed of 10 m / s or more and 20 m / s or less.

After steam stripping, it is preferable to carry out a method of extrusion-drying the rubber composition and hot-air drying as described in International Publication No. 2013-146530.
These make it possible to obtain porous granular crumbs.
The particle size of the metal or metal compound in the rubber composition is such that it is difficult to contaminate the molding mold, the peel resistance of the rubber composition from the veil molded body, and the smoothness when the rubber composition for cross-linking is made into a sheet. From the viewpoint of balance, out of 100 vol% of the total volume of the particles of the metal or the metal compound, 60 vol% or more is preferably 0.1 to 90 μm, and 80 vol% or more is more preferably the particle size range.
The particle size of the particles of the metal or the metal compound in the rubber composition is analyzed by a laser diffraction type particle size distribution meter of a polymer solution obtained by dissolving the rubber composition containing the metal or the metal compound in an inert solvent. It can be measured by this.
The particle size of the crumb is preferably 0.1 mm or more, more preferably 0.5 mm or more, from the viewpoint of obtaining the desorption resistance of the rubber composition from the molded product and the scattering resistance at the time of drying.
On the other hand, the particle size of the crumb is preferably 30 mm or less, more preferably 20 mm or less, from the viewpoint of the drying property of the residual solvent and water in the crumb and the expansion resistance of the molded product after molding of the rubber composition.
As a method for adjusting the particle size of the crumb, there are a case where the grain size is adjusted in the process of removing the solvent and drying, and a case where the manufactured crumb is processed and adjusted.
The case of adjusting in the process of removing the solvent and drying the crumb is not particularly limited, but for example, a method for adjusting the molecular weight, composition and structure of the rubber-like polymer (A), the rubber-like polymer (A). A method of adjusting the amount of the rubber softening agent (D) added to the solution, a method of adjusting the hole diameter of the die of the extruder, and a method of adding the solution of the rubber-like polymer (A) to hot water to remove the solvent. Examples include a method of adjusting the conditions at the time.
When the produced crumb is processed and adjusted, the method is not particularly limited, and examples thereof include a method of sieving the crumb and a method of crushing and crushing the crumb with a mixer or a granulator.

The specific surface area of the crumb of the rubber composition of the present embodiment is preferably 0.7 to 3.2 m ² / g, more preferably 1.0 to 3.0 m ² / g, from the viewpoint of handleability. ..
When the specific surface area of the crumbs is 0.7 m ² / g or more, the area in which one crumb is in close contact with the crumbs around the molded body during molding also increases, so that the crumbs are less likely to peel off from the molded body. When the specific surface area of the crumbs is 3.2 m ² / g or less, the crumb particles are compressed at a higher density when molded, and the voids between the crumbs are suppressed, so that the expansion of the molded body can be suppressed.
The method for adjusting the specific surface area of the crumbs to the above range is not particularly limited, and examples thereof include a method of sifting the crumbs and adjusting the composition of each sifted crumb.

The residual solvent in the rubber composition of the present embodiment is preferably low from the viewpoint of reducing odor and VOC. It is preferably 5000 ppm or less, more preferably 3000 ppm or less, and even more preferably 1500 ppm or less. Further, from the viewpoint of economic balance, 50 ppmm or more is preferable, 150 ppm or more is more preferable, and 300 ppm or more is further preferable.

(Moisture in the rubber composition of the veil molded product)
The water content in the rubber composition of the veil molded product of the present embodiment is preferably 0.05% by mass or more and 1.5% by mass or less.
The water content in the rubber composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of suppressing gel during drying after removing the solvent and suppressing a decrease in yield due to powder formation. , 0.2% by mass or more is more preferable. On the other hand, from the viewpoint of suppressing dew condensation of the rubber composition, 1.5% by mass or less is preferable, 1.0% by mass or less is more preferable, and 0.8% by mass or less is further preferable.
The water content in the rubber composition of the veil molded product of the present embodiment can be controlled within the above numerical range by adjusting the above-mentioned crumb shape and the conditions of the drying step.

[Molded product]
The veil molded product of the present embodiment is the molded product of the rubber composition of the present embodiment described above, and is preferably a block-shaped molded product from the viewpoint of handleability.
The bale molded product of the present embodiment is more preferably a block-shaped (bale) molded product having a size of 1,000 cm ³ or more. Further, it is even more preferable that the bale-molded body is a rectangular parallelepiped type having a weight of 17.5 kg to 35 kg.

As a method for forming the bale molded product of the present embodiment, there are a method of compressing crumbs and a method of producing sheets and stacking and compressing the sheets. As a forming method, the specific surface area is 0.7 m ² / g. A method of producing a crumb of about 3.2 m ² / g and compression molding the crumb is preferable. From the viewpoint of moldability, it is preferable to further carry out a step of sieving the crumbs before molding.
Since the crumbs are in close contact with each other when the crumbs are compression-molded, the specific surface area of the molded product is lower than the specific surface area of the crumbs. The adhesion of the crumb during compression molding can be adjusted by the molecular weight, composition and structure of the rubber-like polymer (A), the composition of the softener for rubber, the temperature during compression, and the pressure. For example, if it is desired to increase the adhesion of the crumb and reduce the specific surface area of the bale, the conditions of lowering the molecular weight of the rubber-like polymer (A), increasing the amount of the softener for rubber, and raising the temperature and pressure during compression are required. preferable.

The specific surface area of the bale molded product of the present embodiment is preferably 0.005 to 0.05 m ² / g, and more preferably 0.01 to 0.04 m ² / g from the viewpoint of film packaging. When the specific surface area of the bale molded body is 0.005 m ² / g or more, the expansion of the bale is suppressed, and when the specific surface area of the bale molded body is 0.05 m ² / g or less, the crumb from the bale molded body It is preferable because peeling is reduced.
The specific surface area of the bale molded product can be determined by the BET method.
Generally, the specific surface area of a large-sized bale-molded product tends to differ depending on the position, so it is preferable to collect the material from the vicinity of the central portion of the veil-molded product.

It is preferable that the rubber composition crumb of the present embodiment is sieved according to the particle size before being molded into a veil molded product, and then mixed in an appropriate amount ratio.
If the specific surface area of the veil molded body formed by using the desolated crumb as it is exceeds the upper limit of the above range, the crumb composition having a large particle size is increased among the sifted crumbs to form a crumb composition having a small particle size. If the lower limit is not reached, it is preferable to reduce the crumb composition having a large particle size and increase the crumbs having a small particle size.

The molding compression pressure of the veil molded product of the present embodiment is preferably 3 to 30 MPa, more preferably 10 to 20 MPa. When the compression pressure at the time of molding is 30 MPa or less, the device can be designed compactly and the installation efficiency is good. When the compression pressure at the time of molding is 3 MPa or more, the moldability is good. When the moldability is good, the surface of the bale molded product is smooth, there is no peeling of the polymer after the molding process, and expansion after molding tends to be suppressed.

The temperature of the rubber composition at the time of molding is preferably 30 to 120 ° C, more preferably 50 to 100 ° C from the viewpoint of reducing residual solvent and suppressing thermal deterioration.
When the temperature of the rubber composition at the time of molding is 30 ° C. or higher, the moldability is good, while when the temperature is 120 ° C. or lower, gel formation due to thermal deterioration of the rubber composition is suppressed, which is preferable.
The higher the temperature and pressure during molding, the smaller the specific surface area of the bale molded product.
The holding time during molding is preferably 3 to 30 seconds, more preferably 5 to 20 seconds. When the holding time during compression is 30 seconds or less, the production efficiency is good, and when the holding time is 5 seconds or more, the moldability is good.

In order to avoid adhesion between the bale molded bodies, it is preferable to wrap the bale molded body of the present embodiment with a resin film (packaging sheet).
As the type of resin for the film, for example, polyethylene, ethylene copolymer resin, polystyrene, high impact polystyrene, or PET can be used.
From the viewpoint of handleability during transportation of the molded body and the fact that dew condensation is unlikely to occur in the gap between the packaging sheet and the bale molded body, it is preferable that the packaging sheet has good adhesion to the bale molded body.
The veil molded product of the present embodiment is used, for example, for storage in a container for transportation. When the expansion rate of the bale molded product one day after molding is less than 5%, the storability in the container is good, which is preferable.

[Rubber composition for cross-linking]
From the viewpoint of high mechanical strength and the like, the rubber composition of the veil-molded body of the present embodiment is preferably used for various purposes by adding a cross-linking agent to obtain a rubber composition for cross-linking, and after cross-linking, to form a cross-linked body.
The cross-linking rubber composition of the present embodiment contains at least the above-mentioned rubber composition of the present embodiment and a cross-linking agent, and may further contain other rubber components, fillers and the like, if necessary.
The other rubber components are not particularly limited and may be appropriately selected depending on the intended purpose. For example, styrene-butadiene rubber (emulsified polymer tire or solution polymerization type), natural rubber, polyisoprene, butadiene rubber, acrylonitrile-butadiene rubber (NBR), chloroprene rubber, ethylene-propylene rubber (EPM), ethylene-propylene-non-conjugated Examples thereof include ethylene rubber (EPDM), butyl rubber, polysulfide rubber, silicone rubber, fluororubber, urethane rubber and the like.
These may be used individually by 1 type, or may be used by mixing 2 or more types.

The content of the rubber-like polymer (A) in the cross-linking rubber composition of the present embodiment with respect to the total amount of rubber, which is the total amount of the rubber-like polymer (A) and other rubber components, has the effect of the present invention. From the viewpoint of exerting, it is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and further preferably 80% by mass or more.

Further, in the cross-linking rubber composition of the present embodiment, a filler can be added as needed for the purpose of improving the reinforcing property.
The blending amount of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is 10 to 10 to 100 parts by mass of the rubber component, which is the total of the rubber-like polymer (A) and other rubbers. 100 parts by mass is preferable, and 20 to 80 parts by mass is more preferable.
When the amount of the filler is 10 parts by mass or more, the effect of improving the reinforcing property by blending the filler can be obtained, and when it is 100 parts by mass or less, the fuel efficiency when the tire is used can be obtained. Good workability can be maintained while avoiding a significant decrease in fuel consumption.

The filler is not particularly limited, and is carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, titanium oxide. , Potassium titanate, barium sulfate and the like, and among these, carbon black is preferably used. These may be used alone or in combination of two or more.
The carbon black is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include FEF, GPF, SRF, HAF, N339, IISAF, ISAF and SAF. These may be used alone or in combination of two or more.
The nitrogen adsorption specific surface area of the carbon black (measured according to N2SA, JIS K6217-2: 2001) is not particularly limited and may be appropriately selected depending on the intended purpose.
When the cross-linking rubber composition of the present embodiment is used as a fuel-efficient tire tread composition, sedimentable silica is preferably used as a filler.

The rubber composition for cross-linking of the present embodiment may contain a silane coupling agent from the viewpoint of improving the dispersibility of the filler and the tensile strength of the cross-linked body.
The silane coupling agent has a function of closely interacting with the rubber component and the inorganic filler, and has an affinity or binding group for each of the rubber component and the silica-based inorganic filler. , A compound having a sulfur-bonded moiety and an alkoxysilyl group or a silanol group moiety in one molecule is preferable.
Such compounds include, but are not limited to, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis-. [2- (Triethoxysilyl) -ethyl] -tetrasulfide, S- [3- (triethoxysilyl) -propyl] octanethioate and S- [3- (triethoxysilyl) -propyl] octanethioate and [ Condensations of (triethoxysilyl) -propyl] thiols, silanes carrying at least one thiol (-SH) functional group (referred to as mercaptosilane) and / or at least one masked thiol group. ..
The content of the silane coupling agent in the cross-linking rubber composition of the present embodiment is preferably 0.1 part by mass or more and 30 parts by mass or less, and 0.5 part by mass or more, with respect to 100 parts by mass of the above-mentioned filler. 20 parts by mass or less is more preferable, and 1.0 part by mass or more and 15 parts by mass or less is further preferable. When the content of the silane coupling agent is in the above range, the effect of the addition by the silane coupling agent tends to be more remarkable.

The cross-linking rubber composition of the present embodiment contains a cross-linking agent.
The cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sulfur-based cross-linking agent, an organic peroxide-based cross-linking agent, an inorganic cross-linking agent, a polyamine cross-linking agent, a resin cross-linking agent, and sulfur. Examples thereof include a compound-based cross-linking agent and an oxymunitrosoamine-based cross-linking agent, and these may be used in combination.
Of these, a sulfur-based cross-linking agent (vulcanizing agent) is more preferable as the rubber composition for tires. Sulfur is particularly preferred.

The content of the cross-linking agent in the cross-linking rubber composition of the present embodiment is 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component. The content of the cross-linking agent is preferably 0.1 part by mass or more, more preferably 0.5 parts by mass or more, and 1.5 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of high tensile strength and high cross-linking speed. More than a portion is more preferable. On the other hand, from the viewpoint of suppressing cross-linking unevenness and high tensile strength, 20 parts by mass or less is preferable, 5 parts by mass or less is more preferable, and 3 parts by mass or less is further preferable.
The rubber component also includes the above-mentioned rubber-like polymer (A) and other rubber components.

In the rubber composition for crosslinking of the present embodiment, a vulcanization accelerator may be further used in combination with the vulcanization agent.
Examples of the vulcanization accelerator include guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and zantate-based compounds. ..

Further, the cross-linking rubber composition of the present embodiment includes other softeners, fillers, heat-resistant stabilizers, antistatic agents, weather-resistant stabilizers, antiaging agents, colorants, lubricants, etc. other than the above-mentioned components. Various additives may be used.
As other softeners, known softeners can be used.
Other fillers include, for example, calcium carbonate, magnesium carbonate, aluminum sulphate, barium sulphate.
Known materials can be used as the heat-resistant stabilizer, antistatic agent, weather-resistant stabilizer, anti-aging agent, colorant, and lubricant.

(Method of kneading rubber composition for cross-linking)
The rubber composition for cross-linking of the present embodiment is the rubber composition of the present embodiment described above, a cross-linking agent, and if necessary, a silica-based inorganic filler, carbon black or other filler, a silane coupling agent, and a rubber. It can be produced by mixing various additives such as softeners.
The mixing method is not limited to the following methods, and for example, a general mixer such as an open roll, a solvent mixer, a kneader, a single-screw screw extruder, a twin-screw screw extruder, or a multi-screw screw extruder is used. Examples thereof include a melt-kneading method and a method of dissolving and mixing each component and then heating and removing the solvent.
Of these, a melt-kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferable from the viewpoint of productivity and good kneading.
Further, any of a method of kneading the rubber component and other fillers, a silane coupling agent, and an additive at one time and a method of mixing them in a plurality of times can be applied.

[Uses of rubber compositions and molded products]
The rubber composition and the rubber composition for cross-linking of the present embodiment can be used, for example, for tire members, interior and exterior parts of automobiles, anti-vibration rubber, belts, footwear, foams, various industrial products and the like.
Among these, it is preferably used for tire parts.
As tire members, for example, various tires such as fuel-saving tires, all-season tires, high-performance tires, snow tires, and studless tires: can be used for various tire parts such as treads, carcass, sidewalls, and bead parts. be. In particular, as a tire member, when it is made into a vulcanized material, it has an excellent balance between wear resistance, fuel efficiency, wet skid resistance and snow performance, so it is a fuel-efficient tire, a high-performance tire, and a snow tire. It is suitably used for tire treads.
As a method for manufacturing a tire, a conventional method can be used. For example, a member used for normal tire manufacturing such as a carcass layer, a belt layer, and a tread layer composed of at least one selected from the group consisting of an unvulcanized rubber composition for cross-linking and a tire cord on a tire forming drum. Stack them one after another and remove the drums to make green tires. Then, by heating and vulcanizing this green tire according to a conventional method, a desired tire (for example, a pneumatic tire) can be manufactured.

Hereinafter, the present embodiment will be described in more detail with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples and comparative examples.
Various physical properties in Examples and Comparative Examples were measured by the methods shown below.

[Physical characteristics of rubber-like polymer (A)]
(Weight average molecular weight (Mw) of the rubber-like polymer (A) before hydrogenation)
Chromatograms were measured using a GPC measuring device in which three columns using polystyrene gel as a filler were connected, and the weight average of the rubbery polymer before hydrogenation was measured based on the calibration curve using standard polystyrene. The molecular weight (Mw) was determined.
The eluent used was THF (tetrahydrofuran) containing 5 mmol / L triethylamine.
As the column, a guard column: a product name "TSKguardcool SuperH-H" manufactured by Tosoh Corporation, and a column: a product name "TSKgel SuperH5000", "TSKgel SuperH6000", and "TSKgel SuperH7000" manufactured by Tosoh Corporation were used.
An RI detector (trade name "HLC8020" manufactured by Tosoh Corporation) was used under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 0.6 mL / min. 10 mg of the sample for measurement was dissolved in 20 mL of THF to prepare a measurement solution, and 20 μL of the measurement solution was injected into a GPC measuring device for measurement.

(Polymer Mooney viscosity of rubber-like polymer (A) before hydrogenation)
Using a rubber-like polymer before hydrogenation as a sample, Mooney viscosity was measured using a Mooney viscometer (trade name "VR1132" manufactured by Ueshima Seisakusho Co., Ltd.) in accordance with ISO 289 and using an L-shaped rotor.
The measurement temperature was 100 ° C.
First, the sample was preheated at the test temperature for 1 minute, then the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain Mooney viscosity (ML _{(1 + 4)} ).

(Degradation rate of rubber-like polymer (A))
The modification rate of the rubber-like polymer (A) was measured by the column adsorption GPC method as follows. The measurement was carried out by utilizing the property that the rubber-like polymer modified with the nitrogen atom-containing functional group is adsorbed on the column.
The amount of adsorption of the sample solution containing the rubbery polymer and low molecular weight internal standard polystyrene to the silica-based column was measured from the difference between the chromatogram measured on the polystyrene-based column and the chromatogram measured on the silica-based column. The degeneration rate was determined.
Specifically, it is as shown below.
Preparation of sample solution:
10 mg of the rubbery polymer and 5 mg of standard polystyrene were dissolved in 20 mL of THF to prepare a sample solution.
GPC measurement conditions using polystyrene columns:
Using THF containing 5 mmol / L triethylamine as an eluent, 20 μL of the sample solution was injected into the device for measurement. As the column, a guard column: a product name "TSKguardcool SuperH-H" manufactured by Tosoh Corporation, and a column: a product name "TSKgel SuperH5000", "TSKgel SuperH6000", and "TSKgel SuperH7000" manufactured by Tosoh Corporation were used. A chromatogram was obtained by measurement using a RI detector (HLC8020 manufactured by Tosoh Corporation) under the conditions of a column oven temperature of 40 ° C. and a THF flow rate of 0.6 mL / min.
GPC measurement conditions using a silica-based column:
Using the trade name "HLC-8320GPC" manufactured by Tosoh Corporation, using THF as an eluent, injecting 50 μL of the sample solution into the device, RI at a column oven temperature of 40 ° C. and a THF flow rate of 0.5 ml / min. Chromatograms were obtained using the detector. The column is used by connecting the product names "Zorbax PSM-1000S", "PSM-300S", and "PSM-60S", and the product name "DIOL 4.6 x 12.5 mm 5 micron" is used as a guard column in front of the column. Used by connecting.
How to calculate the denaturation rate:
A sample with the total peak area of the chromatogram using a polystyrene-based column as 100, the peak area of the sample as P1, the peak area of standard polystyrene as P2, and the total peak area of the chromatogram using a silica-based column as 100. The modification rate (%) was calculated from the following formula, where the peak area of the standard polystyrene was P3 and the peak area of the standard polystyrene was P4.
Degeneration rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100
(However, P1 + P2 = P3 + P4 = 100)

(Amount of bound styrene of rubber-like polymer (A) before hydrogenation)
As a sample, 100 mg of the rubber-like polymer before hydrogenation was added up to 100 mL with chloroform and dissolved to prepare a measurement sample. Measuring device: Shimadzu Seisakusho measured the amount of bonded styrene (% by mass) with respect to 100% by mass of the rubber-like polymer before hydrogenation as a sample, based on the amount of ultraviolet absorption wavelength (around 254 nm) absorbed by the phenyl group of styrene. A spectrophotometer "UV-2450" manufactured by the same company was used.

(Microstructure of butadiene portion of rubber-like polymer (A) before hydrogenation (1,2-vinyl bond amount))
As a sample, 50 mg of the rubber-like polymer before hydrogenation was dissolved in 10 mL of carbon disulfide to prepare a measurement sample.
Using a solution cell, the infrared spectrum is measured in the range of 600 to 1000 cm ^-1 and the absorbance at a given wave number is used by Hampton's method (method according to RR Hampton, Analytical Chemistry 21, 923 (1949)). The microstructure of the butadiene moiety, that is, the 1,2-vinyl bond amount (mol%) was determined according to the above formula.
Measuring device: A Fourier transform infrared spectrophotometer "FT-IR230" manufactured by JASCO Corporation was used.

(Amount of styrene block of rubber-like polymer (A))
A chain in which 8 or more styrene structural units were connected was defined as a styrene block, and was obtained as follows.
From the ¹ H-NMR spectrum of 400 MHz measured using deuterated chloroform as a solvent, the integral value ratio of each chemical shift range in (a) below was determined, and the content of the styrene block contained in the rubber-like polymer was determined.
(A) Aromatic vinyl compound chain 8 or more: 6.00 ≦ S <6.68

(Iodine value of rubber-like polymer (A))
The iodine value of the rubbery polymer (A) was calculated according to the method described in "JIS K 0070: 1992".

(Amount of bound styrene of rubber-like polymer (A) (after hydrogenation), ethylene structure, conjugated diene unit)
Using the rubbery polymer (A) as a sample, the amount of bound styrene (after hydrogenation), the ethylene structure, and the unit amount of conjugated diene were measured by ¹ H-NMR measurement. ¹ The conditions for 1 H-NMR measurement are described below.
<Measurement conditions>
Measuring equipment: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform measurement sample: Rubber polymer sample concentration: 50 mg / mL
Observation frequency: 400MHz
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C

[Physical characteristics of rubber composition]
(Metal content of rubber composition (Al content, Ti content))
The rubber compositions obtained in Examples and Comparative Examples described later are subjected to elemental analysis using inductively coupled plasma (ICP, Inductively Coupled Plasma, manufactured by Shimadzu Corporation, device name: ICPS-7510) in the rubber composition. Aluminum content (Al content, unit ppm) and titanium content (Ti content, unit ppm) were measured.

(Moisture content of rubber composition)
50 g of the rubber composition was placed in a hot air dryer heated to 150 ° C., dried for 3 hours, and the difference in mass of the rubber composition before and after drying was measured to determine the water content of the rubber composition.

[Evaluation of molded product of rubber composition]
(Method of removing solvent from rubber composition solution)
<Solvent removal condition 1>
Assuming steam stripping, 20 L of hot water at 90 ° C is placed in a 50 L container, and the polymer solution is stirred with a homogenizer (homogenizer MARKII (PRIMIX Co., Ltd., trade name, 0.2 kW) at a rotation speed of 1000 rpm). The solvent was removed by dropping the solution at a rate of 200 g per minute for 30 minutes and continuing stirring for 30 minutes after the completion of the dropping. Obtained.

<Solvent removal condition 2>
Assuming steam stripping, 20 L of hot water at 90 ° C is placed in a 50 L container, and the polymer solution is stirred with a homogenizer (homogenizer MARKII (PRIMIX Co., Ltd., trade name, 0.2 kW) at a rotation speed of 12000 rpm). The solvent was removed by dropping the solution at a rate of 200 g per minute for 30 minutes and continuing stirring for 30 minutes after the completion of the dropping. Obtained.

(Forming method of veil of rubber composition)
A rectangular container with dimensions of 210 mm on the long side, 105 mm on the short side, and 200 mm in depth is filled with the crumb prepared by the above method after heating to 60 ° C., and a pressure of 3.5 MPa is compressed in a cylinder over 10 seconds. And a veil of rubber composition was obtained.

(Evaluation: Increased Mooney viscosity resistance of rubber composition)
The Mooney viscosity of the rubber composition was measured under the following conditions.
The Mooney viscosity was measured using an L-shaped rotor in accordance with ISO 289 using a Mooney viscometer (trade name "VR1132" manufactured by Ueshima Seisakusho Co., Ltd.).
The measurement temperature was 100 ° C.
First, the sample was preheated at the test temperature for 1 minute, then the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain Mooney viscosity (ML _{(1 + 4)} ).
The difference between the Mooney viscosity measured within 4 hours after obtaining the rubber composition and the Mooney viscosity after storage at 25 ° C. and 30% humidity for 1 month was evaluated as ΔML.
If ΔML is 0 or more and less than 4, it is evaluated as ⊚, if it is 4 or more and less than 8, it is evaluated as ◯, if it is 8 or more and less than 15, it is evaluated as Δ, and if it is 15 or more, it is evaluated as ×.
Practically, it is necessary to be less than 15, and preferably less than 8.

(Evaluation: Contamination resistance of molding dies)
When the bale molded product was molded 10 times under the above conditions, the number of times that a total of 5 g or more of metal or crumb was attached to the rectangular container was evaluated. If the total number of times that 5 g or more of metal or crumb is attached is 0 times, it is marked with ⊚, if it is 1 to 2 times, it is marked with ◯, if it is 3 to 4 times, it is marked with Δ, and if it is 5 times or more, it is marked with ×. Practically, it is necessary to be 4 times or less, and preferably 2 times or less.

(Evaluation: Peeling resistance of rubber composition from veil molded product)
Using the bale-molded body molded under the above conditions, the amount of crumbs peeled off from the bale-molded body was determined by a bale drop test.
Specifically, the amount of crumbs peeled off from the bale molded body when the bale molded body was dropped vertically from a height of 100 cm onto the concrete floor surface was measured.
The smaller the amount of the crumbs that have peeled off, the smaller the amount of crumbs that have peeled off from the bale molded product after the molding step of the actual manufacturing process, which is preferable.
If this amount is less than 0.05% by mass of the total amount of the bale molded body, it is ⊚, if it is 0.05% by mass or more and less than 0.1% by mass, it is 〇, and if it is 0.01% by mass or more and less than 0.2% by mass. And Δ, if 0.2% by mass or more, it was evaluated as ×.
Practically, it needs to be less than 0.2% by mass, preferably less than 0.1% by mass.

(Evaluation: Adhesion of veil molded product to packaging sheet)
A polyethylene film is adhered on an iron plate, the bale molded body is placed on the polyethylene film, a load of 5 kg is applied at an outside temperature of 25 ° C. and a humidity of 50%, and the mixture is left for 72 hours to improve the adhesion between the polyethylene film and the bale molded body. evaluated.
Specifically, the iron plate was gradually tilted from the state where the bale molded body on the iron plate was left still, and finally tilted until the angle between the iron plate and the ground became 90 degrees, and then left in that state. ..
When the bale molded body does not fall for 10 seconds or more when the angle between the ground and the iron plate is 90 degrees ◎, when the bale molded body falls within 1 second or more and less than 10 seconds when the angle between the ground and the iron plate is 90 degrees 〇, If the angle between the ground and the iron plate falls between 75 degrees and less than 90 degrees, or if it falls within 1 second after reaching 90 degrees △, the angle between the ground and the iron plate falls between 0 degrees and less than 75 degrees. Case x.
Practically, it is necessary that the veil molded body does not fall until the angle between the ground and the iron plate is 75 degrees or more.

[Preparation of hydrogenation catalyst, rubbery polymer (A), rubber composition]
(Preparation of hydrogenation catalyst)
In Examples and Comparative Examples described later, a hydrogenation catalyst used for preparing a rubbery polymer was prepared by the following method.
<Manufacturing example 1>
2 liters of dried and purified cyclohexane were placed in a nitrogen-substituted reaction vessel, and 40 mmol of bis (η5-cyclopentadienyl) titanium di- (p-tolyl) and 1,2-polybutadiene having a molecular weight of about 1,000 were placed therein. (1,2-vinyl binding amount about 85%) 150 g was dissolved. Then, a cyclohexane solution containing 60 mmol of n-butyllithium is added to the reaction vessel, the reaction is carried out at room temperature for 5 minutes, and immediately 40 mmol of n-butanol is added and stirred to obtain a hydrogenation catalyst (TC-1). Obtained. The obtained catalyst was stored at room temperature.

<Manufacturing example 2>
1 liter of dried and purified cyclohexane is charged in a hydrogenated reaction vessel, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride is added, and an n-hexane solution containing 200 mmol of trimethylaluminum is added with sufficient stirring. Then, the reaction was carried out at room temperature for about 3 days to obtain a hydrogenation catalyst (TC-2).

(Polymerization of rubber-like polymer (A))
<(Polymerization Example 1) Rubber-like polymer (S) before hydrogenation>
An autoclave with an internal volume of 40 L and a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were removed in advance. 1,3-butadiene was 2,160 g, styrene was 300 g, and cyclohexane was 21, 000 g, 30 mmol of tetrahydrofuran (THF) and 3.6 mmol of 2,2-bis (2-oxolanyl) propane as polar substances were placed in the reactor, and the temperature inside the reactor was maintained at 46 ° C.
As a polymerization initiator, 23.9 mmol of n-butyllithium was supplied to the reactor.
After the start of the polymerization reaction, the temperature inside the reactor began to rise due to the heat generated by the polymerization, and after the monomer conversion in the reactor reached 98%, 540 g of 1,3-butadiene was added and reacted.
The temperature in the final reactor reached 76 ° C. Two minutes after reaching this reaction temperature peak, 9.0 mmol of N-benzylidene-3- (trimethoxysilyl) -1-propaneamine (Compound 1) was added to the reactor, and the coupling reaction was carried out for 20 minutes. .. To this polymer solution, 5.5 mmol of methanol was added as a reaction terminator to obtain a rubbery polymer solution (SS).
A part of the rubber-like polymer solution before hydrogenation was withdrawn and the solvent was removed with a dryer to obtain a rubber-like polymer (S) before hydrogenation.
The results of the analysis are shown in Table 1.

<(Polymerization Example 2) Rubber-like polymer (T) before hydrogenation>
An autoclave with an internal volume of 40 L and a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were removed in advance. 1,3-butadiene was 2,100 g, styrene was 780 g, and cyclohexane was 21, 000 g, 30 mmol of tetrahydrofuran (THF) and 15.4 mmol of 2,2-bis (2-oxolanyl) propane as polar substances were placed in the reactor, and the temperature inside the reactor was maintained at 42 ° C.
As a polymerization initiator, 21.1 mmol of n-butyllithium was supplied to the reactor.
After the start of the polymerization reaction, the temperature inside the reactor began to rise due to the heat generated by the polymerization, and after the monomer conversion in the reactor reached 98%, 120 g of 1,3-butadiene was added and reacted.
The temperature in the final reactor reached 78 ° C. Two minutes after reaching this reaction temperature peak, 7.9 mmol of N-benzylidene-3- (trimethoxysilyl) -1-propaneamine (Compound 1) was added to the reactor, and the coupling reaction was carried out for 20 minutes. .. To this polymer solution, 4.8 mmol of methanol was added as a reaction terminator to obtain a rubbery polymer solution (TS).
A part of the rubber-like polymer solution before hydrogenation was withdrawn and the solvent was removed with a dryer to obtain a rubber-like polymer (T) before hydrogenation.
The results of the analysis are shown in Table 1.

<(Polymerization Example 3) Rubber-like polymer (U) before hydrogenation>
A temperature-controllable autoclave with an internal volume of 40 L and a stirrer and a jacket was used as a reactor, and impurities were removed in advance. 450 g of styrene, 21,000 g of cyclohexane, and tetrahydrofuran (THF) as a polar substance. 30 mmol and 2,2-bis (2-oxolanyl) propane were placed in a reactor at 6.2 mmol, and the temperature inside the reactor was maintained at 44 ° C.
As a polymerization initiator, 24.4 mmol of n-butyllithium was supplied to the reactor.
After the start of the polymerization reaction, the temperature inside the reactor began to rise due to the heat generated by the polymerization, and after the monomer conversion in the reactor reached 98%, 2,220 g of 1,3-butadiene was added, and 1 minute from the completion of the addition. Later, 120 g of styrene was added and reacted.
The temperature in the final reactor reached 78 ° C. Two minutes after reaching this reaction temperature peak, 9.1 mmol of N-benzylidene-3- (trimethoxysilyl) -1-propaneamine (Compound 1) was added to the reactor, and the coupling reaction was carried out for 20 minutes. .. To this polymer solution, 5.6 mmol of methanol was added as a reaction terminator to obtain a rubbery polymer solution (US).
A part of the rubber-like polymer solution (US) before hydrogenation was withdrawn and the solvent was removed with a dryer to obtain a rubber-like polymer (U) before hydrogenation.
The results of the analysis are shown in Table 1.

<(Polymerization Example 4) Rubber-like polymer (V) before hydrogenation>
A temperature-controllable autoclave with an internal volume of 40 L and a stirrer and a jacket was used as a reactor, and impurities were removed in advance. 1,3-butadiene was 3,000 g, cyclohexane was 21,000 g, and a polar substance. As a result, 30 mmol of tetrahydrofuran (THF) and 4.5 mmol of 2,2-bis (2-oxolanyl) propane were placed in the reactor, and the temperature inside the reactor was maintained at 41 ° C.
As a polymerization initiator, 30.0 mmol of n-butyllithium was supplied to the reactor.
After the start of the polymerization reaction, the temperature inside the reactor began to rise due to the heat generated by the polymerization, and the final temperature inside the reactor reached 80 ° C. Two minutes after reaching this reaction temperature peak, 11.2 mmol of N-benzylidene-3- (trimethoxysilyl) -1-propaneamine (Compound 1) was added to the reactor, and the coupling reaction was carried out for 20 minutes. .. To this polymer solution, 6.9 mmol of methanol was added as a reaction terminator to obtain a rubbery polymer solution (VS).
A part of the rubber-like polymer solution before hydrogenation was withdrawn and the solvent was removed with a dryer to obtain a rubber-like polymer (V) before hydrogenation.
The results of the analysis are shown in Table 1.

<(Polymerization Example 5) Rubber-like polymer (W) before hydrogenation>
An autoclave with an internal volume of 40 L and a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were removed in advance. 1,3-butadiene was 2,160 g, styrene was 300 g, and cyclohexane was 21, 000 g, 30 mmol of tetrahydrofuran (THF) and 1.4 mmol of 2,2-bis (2-oxolanyl) propane as polar substances were placed in the reactor, and the temperature inside the reactor was maintained at 48 ° C.
12.2 mmol of n-butyllithium was supplied to the reactor as a polymerization initiator.
After the start of the polymerization reaction, the temperature inside the reactor began to rise due to the heat generated by the polymerization, and after the monomer conversion in the reactor reached 98%, 540 g of 1,3-butadiene was added and reacted.
The temperature in the final reactor reached 73 ° C. Two minutes after reaching this reaction temperature peak, 4.5 mmol of N-benzylidene-3- (trimethoxysilyl) -1-propaneamine (Compound 1) was added to the reactor, and a coupling reaction was carried out for 20 minutes. .. 3.0 mmol of methanol was added to this polymer solution as a reaction terminator to obtain a rubbery polymer solution (WS).
A part of the rubber-like polymer solution before hydrogenation was withdrawn and the solvent was removed with a dryer to obtain a rubber-like polymer (W) before hydrogenation.
The results of the analysis are shown in Table 1.

<(Polymerization Example 6) Rubber-like polymer (X) before hydrogenation>
An autoclave with an internal volume of 40 L and a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were removed in advance. 1,3-butadiene was 2,160 g, styrene was 300 g, and cyclohexane was 21, 000 g, 30 mmol of tetrahydrofuran (THF) and 3.6 mmol of 2,2-bis (2-oxolanyl) propane as polar substances were placed in the reactor, and the temperature inside the reactor was maintained at 46 ° C.
As a polymerization initiator, 23.9 mmol of n-butyllithium was supplied to the reactor.
After the start of the polymerization reaction, the temperature inside the reactor began to rise due to the heat generated by the polymerization, and after the monomer conversion in the reactor reached 98%, 540 g of 1,3-butadiene was added and reacted.
The temperature in the final reactor reached 76 ° C. Two minutes after reaching this reaction temperature peak, 9.0 mmol of trimethoxymethylsilane (Compound 2) was added to the reactor, and a coupling reaction was carried out for 20 minutes. To this polymer solution, 5.5 mmol of methanol was added as a reaction terminator to obtain a rubbery polymer solution (XS).
A part of the rubber-like polymer solution before hydrogenation was withdrawn and the solvent was removed with a dryer to obtain a rubber-like polymer (X) before hydrogenation.
The results of the analysis are shown in Table 1.

(Preparation of rubber composition)
<(Example 1) Rubber composition (SH-1)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 50 minutes to obtain a rubbery polymer (S-1). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A thing (SH-1) was obtained.
The results of the analysis are shown in Table 2.

<(Example 2) Rubber composition (SH-2)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out for 100 minutes at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. to obtain a rubbery polymer (S-2). The iodine value of the obtained rubber-like polymer was 38.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. (SH-2) was obtained.
The results of the analysis are shown in Table 2.

<(Example 3) Rubber composition (SH-3)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 110 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 90 ° C. for 50 minutes to obtain a rubbery polymer (S-3). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A thing (SH-3) was obtained.
The results of the analysis are shown in Table 2.

<(Example 4) Rubber composition (SH-4)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 60 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 60 minutes to obtain a rubbery polymer (S-4). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 2>, and the rubber composition was dried by a dryer. A product (SH-4) was obtained.
The results of the analysis are shown in Table 2.

<(Example 5) Rubber composition (TH-1)>
The hydrogenation catalyst (TC-1) prepared in (Production Example 1) above was added to the rubber-like polymer solution (TS) before hydrogenation obtained in (Polymerization Example 2), and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 60 minutes to obtain a rubbery polymer (T-1). The iodine value of the obtained rubber-like polymer was 70.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A thing (TH-1) was obtained.
The results of the analysis are shown in Table 2.

<(Example 6) Rubber composition (SH-5)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 100 minutes to obtain a rubbery polymer (S-5). The iodine value of the obtained rubber-like polymer was 38.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, and at the same time adding 150 g of SRAE oil (JOMO process NC140 manufactured by JX Nikko Nisseki Energy Co., Ltd.) and mixing, 6000 g of the rubber composition solution was added as described above. The solvent was removed by the method of solvent condition 1> and dried by a dryer to obtain a rubber composition (SH-5).
The results of the analysis are shown in Table 2.

<(Example 7) Rubber composition (SH-6)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 50 minutes to obtain a rubbery polymer (S-6). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol and 6 g of stearic acid at the same time, the solvent of 6000 g of the rubber composition solution was removed by the method of <solvent removal condition 1>, and the dryer was used. The rubber composition (SH-6) was obtained.
The results of the analysis are shown in Table 3.

<(Example 8) Rubber composition (SH-7)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 50 minutes to obtain a rubbery polymer (S-7). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. It was taken out in half the time as compared with the above (Example 1) to obtain a rubber composition (SH-7).
The results of the analysis are shown in Table 3.

<(Example 9) Rubber composition (TH-2)>
The hydrogenation catalyst (TC-1) prepared in (Production Example 1) above was added to the rubber-like polymer solution (TS) before hydrogenation obtained in (Polymerization Example 2), and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 40 minutes to obtain a rubbery polymer (T-2). The iodine value of the obtained rubber-like polymer was 129.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A thing (TH-2) was obtained.
The results of the analysis are shown in Table 3.

<(Example 10) Rubber composition (SH-8)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubbery polymer solution (SS) before hydrogenation obtained in the above (Polymerization Example 1), and the rubbery polymer before hydrogenation was added. 69 ppm based on titanium was added per 100 parts by mass, and the hydrogenation catalyst (TC-2) prepared in the above (Production Example 2) was added at 1 ppm (based on titanium) per 100 parts by mass of the rubbery polymer before hydrogen addition. 2 ppm) was added based on aluminum, and the hydrogenation reaction was carried out for 50 minutes at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. to obtain a rubbery polymer (S-8). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 2>, and the rubber composition was dried by a dryer. A product (SH-8) was obtained.
The results of the analysis are shown in Table 3.

<(Example 11) Rubber composition (WH-1)>
The hydrogenation catalyst (TC-1) prepared in (Production Example 1) above was added to the rubber-like polymer solution (WS) before hydrogenation obtained in (Polymerization Example 5), and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 80 ° C. for 70 minutes to obtain a rubbery polymer (W-1). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, and simultaneously adding 1050 g of SRAE oil (JOMO process NC140 manufactured by JX Nikko Nisseki Energy Co., Ltd.) and mixing, 6000 g of the rubber composition solution was added to the above <. The solvent was removed by the method of solvent removal condition 1>, and a drying treatment was performed with a dryer to obtain a rubber composition (WH-1).
The results of the analysis are shown in Table 3.

<(Example 12) Rubber composition (XH-1)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (XS) obtained in the above (Polymerization Example 6) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 80 ° C. for 70 minutes to obtain a rubbery polymer (X-1). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A product (XH-1) was obtained.
The results of the analysis are shown in Table 3.

<(Comparative Example 1) Rubber Composition (SH-9)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubbery polymer solution (SS) before hydrogenation obtained in the above (Polymerization Example 1), and the rubbery polymer before hydrogenation was added. 66 ppm based on titanium was added per 100 parts by mass, and the hydrogenation catalyst (TC-2) prepared in the above (Production Example 2) was added at 4 ppm (based on titanium) per 100 parts by mass of the rubbery polymer before hydrogen addition. 8 ppm) was added based on aluminum, and the hydrogenation reaction was carried out for 50 minutes at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. to obtain a rubbery polymer (S-9). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A thing (SH-9) was obtained.
The results of the analysis are shown in Table 4.

<(Comparative Example 2) Rubber Composition (SH-10)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 150 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 90 ° C. for 40 minutes to obtain a rubbery polymer (S-10). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A product (SH-10) was obtained.
The results of the analysis are shown in Table 4.

<(Comparative Example 3) Rubber Composition (TH-3)>
The hydrogenation catalyst (TC-1) prepared in (Production Example 1) above was added to the rubber-like polymer solution (TS) before hydrogenation obtained in (Polymerization Example 2), and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 40 minutes to obtain a rubbery polymer (T-3). The iodine value of the obtained rubber-like polymer was 156.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A thing (TH-3) was obtained.
The results of the analysis are shown in Table 4.

<(Comparative Example 4) Rubber Composition (UH-1)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubbery polymer solution (US) before hydrogenation obtained in (Polymerization Example 3), and the rubbery polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 85 ° C. for 60 minutes to obtain a rubbery polymer (U-1). The iodine value of the obtained rubber-like polymer was 70.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A thing (UH-1) was obtained.
The results of the analysis are shown in Table 4.

<(Comparative Example 5) Rubber Composition (VH-1)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (VS) obtained in the above (Polymerization Example 4) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 70 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.9 MPa and an average temperature of 85 ° C. for 120 minutes to obtain a rubbery polymer (V-1). The iodine value of the obtained rubber-like polymer was 9.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 1>, and the rubber composition was dried by a dryer. A product (VH-1) was obtained.
The results of the analysis are shown in Table 4.

<(Comparative Example 6) Rubber Composition (SH-11)>
The hydrogenation catalyst (TC-1) prepared in the above (Production Example 1) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 8 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 1.8 MPa and an average temperature of 75 ° C. for 200 minutes to obtain a rubbery polymer (S-11). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. After adding 3.0 g of (octylthiomethyl) -o-cresol, the solvent was removed from 6000 g of the rubber composition solution by the method of the above <solvent removal condition 2>, and the rubber composition was dried by a dryer. A thing (SH-11) was obtained.
The results of the analysis are shown in Table 4.

<(Comparative Example 7) Rubber Composition (SH-12)>
The hydrogenation catalyst (TC-2) prepared in the above (Production Example 2) was added to the rubber-like polymer solution (SS) obtained in the above (Polymerization Example 1) before hydrogenation, and the rubber-like polymer before hydrogenation was added. 100 ppm was added per 100 parts by mass based on titanium, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and an average temperature of 90 ° C. for 30 minutes to obtain a rubbery polymer (S-12). The iodine value of the obtained rubber-like polymer was 85.
12.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydrooxyphenyl) -propionate as an antioxidant in the obtained rubbery polymer solution and 4,6-bis. 3.0 g of (octylthiomethyl) -o-cresol was added. Further, an aqueous solution prepared by adding N-pyridine oxide dissolved in 2 times mol of ethanol and dissolving 2 times mol citric acid in 2 times volume of water with respect to the polymerization solution with respect to the metal residue. The mixture was added and mixed with a rotary disperser having a meshing structure (Cavitron 1010 manufactured by Nikko Kogyo Co., Ltd.) at 60 ° C. and 7600 rpm for 1 second (sec) to obtain a mixed solution. At this time, the P / V value was 25 × 10 ⁴ (kw / m ³ ), and the peripheral speed was 28 (m / s). Then, the obtained mixed solution was sent to a tank heated to 60 ° C. and allowed to stay for 5 minutes to separate the polymer solution phase and the aqueous phase. After removing the aqueous phase, the polymer solution was vacuum dried to obtain a rubber composition (SH-11). The above-mentioned solvent removal method is shown in Table 4 as <solvent removal condition 3>.
The results of the analysis are shown in Table 4.

In Table 1, the modifier compounds 1 and 2 are shown below.
Compound 1: N-Benzylidene-3- (trimethoxysilyl) -1-propaneamine Compound 2: Trimethoxymethylsilane

[Examples 13 to 15] [Comparative Examples 8 to 11]
[Preparation of rubber composition for cross-linking, evaluation of physical properties]
(Rubber compositions: SH-1 to SH-3, SH-9, TH-3) of (Examples 1 to 3), (Comparative Examples 1), and (Comparative Examples 3 to 5) shown in Tables 2 to 4. , UH-1 and VH-1) as raw material rubber components, respectively, according to the formulation shown below, to obtain a cross-linking rubber composition containing each raw material rubber.

(Rubber component)
-Rubber composition (samples: SH-1 to SH-3, SH-9, TH-3, UH-1, VH-1)
: 80 parts by mass (mass part without softener for rubber)
・ High cis polybutadiene (trade name "UBEPOL BR150" manufactured by Ube Industries, Ltd.)
: 20 parts by mass

(Mixing conditions)
The amount of each compounding agent added is shown by the number of parts by mass with respect to 100 parts by mass of the rubber component containing no softening agent for rubber.
-Silica 1 (trade name "Ultrasil 7000GR" manufactured by Ebonic Degusa, nitrogen adsorption ratio surface area 170 m2 / g): 50.0 parts by mass-Silica 2 (trade name "Zeosil Premium 200MP" manufactured by Rhodia), nitrogen adsorption ratio surface area 220 m2 / g): 25.0 parts by mass ・ Carbon black (trade name “Seast KH (N339)” manufactured by Tokai Carbon Co., Ltd.): 5.0 parts by mass ・ Silane coupling agent (trade name “Si75” manufactured by Ebonic Degusa), Bis (triethoxysilylpropyl) disulfide): 6.0 parts by mass ・ SRAE oil (trade name “Process NC140” manufactured by JX Nikko Nisseki Energy Co., Ltd.): 25.0 parts by mass ・ Zinc flower: 2.5 parts by mass ・Stealic acid: 1.0 part by mass ・ Anti-aging agent (N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine): 2.0 part by mass ・ Sulfur: 2.2 part by mass ・ Addition Sulfurization accelerator 1 (N-cyclohexyl-2-benzothiadylsulfinamide): 1.7 parts by mass ・ Sulfurization accelerator 2 (diphenylguanidine): 2.0 parts by mass ・ Total: 222.4 parts by mass

(Kneading method)
The above materials were kneaded by the following method to obtain a rubber composition.
Using a closed kneader equipped with a temperature control device (content capacity 0.3L), the raw rubber (samples SH-1 to SH) is used as the first stage kneading under the conditions of a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm. -3, SH-9, TH-3, UH-1, VH-1), filler (silica 1, silica 2, carbon black), silane coupling agent, SRAE oil, zinc oxide and stearic acid were kneaded.
At this time, the temperature of the closed mixer was controlled, and the discharge temperature was 155 to 160 ° C. to obtain each rubber composition (blending).
Next, as the second stage kneading, the formulation obtained above was cooled to room temperature, an antiaging agent was added, and the mixture was kneaded again in order to improve the dispersion of silica. Also in this case, the discharge temperature of the compound was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer.
After cooling, sulfur and vulcanization accelerators 1 and 2 were added and kneaded in an open roll set at 70 ° C. for kneading in the third stage. Then, it was molded and vulcanized in a vulcanization press at 160 ° C. for 20 minutes.
The rubber composition before vulcanization and the rubber composition after vulcanization were evaluated. Specifically, it was evaluated by the following method.
The results are shown in Table 5.

(Evaluations 1 and 2) Wet skid resistance and fuel efficiency (viscoelastic parameters)
The viscoelasticity parameters were measured in the torsion mode using a viscoelasticity tester "ARES" manufactured by Leometrics Scientific.
Tan δ measured at 0 ° C. at a frequency of 10 Hz and a strain of 1% was used as an index of wet skid resistance. The larger the index, the better the wet skid resistance.
Tan δ measured at a frequency of 10 Hz and a strain of 3% at 50 ° C. was used as an index of fuel efficiency. The smaller the index, the better the fuel efficiency.
Table 5 below shows symbols when the wet skid resistance and fuel efficiency change within the following range based on the physical properties of the formulation using the rubber composition (SH-9) of (Comparative Example 1). Described.
Δ: From less than 5% deterioration to less than 5% improvement, 〇: 5% or more improvement to less than 15% improvement, ⊚: 15% or more improvement to less than 20% improvement, ×: 5% or more deterioration

(Evaluation 3) Fracture characteristics The breaking strength and breaking elongation were measured according to the tensile test method of JIS K6251. In addition, the product of the measured values of breaking strength and breaking elongation was taken as the breaking characteristic.
Table 5 below shows symbols when the fracture characteristics change within the following range based on the physical properties of the formulation using the rubber composition (SH-9) of (Comparative Example 1).
Δ: Less than 5% deterioration to less than 5% improvement, 〇: 5% or more improvement to less than 15% improvement, ⊚: 15% or more improvement to less than 20% improvement, ×: 5% or more deterioration

As shown in Tables 2 to 4, in Examples 1 to 12, the Mooney fluctuation of the bale molded product of the rubber composition with time was smaller than that of the comparative example, the stain resistance of the molding die, and the bale molded product. It was confirmed that the rubber composition was excellent in peeling resistance and adhesion of the packaging sheet to the bale molded product. It was also confirmed that the small increase in Mooney viscosity makes it difficult for the physical properties to change over time and the quality is stable. In addition, it was confirmed that the molding mold is less likely to be contaminated, so that there is less contamination due to deposits on the mold during bale molding, and the production stability is excellent. Further, it was confirmed that the rubber composition is difficult to peel off from the bale molded body, so that the rubber composition peeled off after bale molding is small, the bale moldability is excellent, and the production stability is excellent. It was also confirmed that the packaging sheet easily adheres to the bale molded product, so that the gap between the packaging sheet and the veil is small and dew condensation is unlikely to occur, and the handling during transportation is excellent.
Further, as shown in Table 5, the cross-linking rubber composition using the rubber compositions of Examples 1 to 3 has the same physical characteristic balance as the cross-linking rubber composition using the rubber composition of Comparative Example 1. From the above, it was confirmed that the rubber composition for crosslinking using the rubber compositions of Comparative Examples 3 to 5 was inferior in the physical property balance.

The veil-molded body of the rubber composition of the present invention is suitable as a constituent material of the rubber composition for cross-linking, and specifically, tire members, automobile interior and exterior parts, anti-vibration rubber, belts, footwear, foams. , Has industrial applicability in fields such as various industrial supplies.

Claims (12)

A rubber-like polymer (A) having an iodine value of 10 to 250, an ethylene structure of ≥3% by mass, and a vinyl aromatic monomer block <10% by mass.
Titanium (C) and
, Containing,
3 ppm ≤ titanium (C) content ≤ 120 ppm,
A veil molded product of a rubber composition having an aluminum (B) content of less than 2 ppm. The rubber-like polymer (A) is a hydrogenated additive of a conjugated diene-based polymer.
The veil molded product according to claim 1. The rubber-like polymer (A) contains 5% by mass or more of vinyl aromatic monomer units.
The veil molded product according to claim 1 or 2. The rubber-like polymer (A) contains a nitrogen atom.
The veil molded product according to any one of claims 1 to 3. The modification rate of the rubber-like polymer (A) measured by the column adsorption GPC method is 40% by mass or more.
The veil molded product according to any one of claims 1 to 4. Further contains 30% by mass or less of the softening agent (D) for rubber.
The veil molded product according to any one of claims 1 to 5. Contains 0.05% by mass or more and 1.5% by mass or less of water.
The veil molded product according to any one of claims 1 to 6. The method for producing a veil-molded rubber composition according to any one of claims 1 to 7.
A step of polymerizing at least a conjugated diene monomer in a solution to obtain a rubbery polymer (A), and
A step of adding titanium (C) to the obtained solution containing the rubber-like polymer (A) to obtain a rubber composition, and
The process of molding the obtained rubber composition and
A method for producing a veil-molded rubber composition. The method for producing a veil molded product according to claim 8, wherein the hydrogenation step is performed using a hydrogenation catalyst having an aluminum content of 0.05 mol or less with respect to 1 mol of titanium content. The solution comprises a step of removing the solvent by steam stripping.
The method for producing a veil molded product according to claim 8 or 9. The rubber composition of the veil molded product according to any one of claims 1 to 7.
With a cross-linking agent,
, Containing,
The cross-linking agent is contained in an amount of 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the rubber component.
Rubber composition for cross-linking. A tread for a tire containing the rubber composition of the veil molded product according to any one of claims 1 to 7.