JP6173021B2 - POLYMER COMPOSITION, RUBBER COMPOSITION, CROSSLINKED RUBBER COMPOSITION, AND METHOD FOR PRODUCING TIRE - Google Patents

Description

The present invention relates to a polymer composition, a rubber composition, a crosslinked rubber composition, and a method for manufacturing a tire.

In recent years, there has been an increasing demand for fuel efficiency reduction of automobiles in connection with the global movement of regulation of carbon dioxide emissions due to increasing interest in environmental problems. In order to meet such demands, tires are required to reduce rolling resistance. As a technique for reducing the rolling resistance of the tire, a technique of applying a low heat-generating rubber composition to the tire can be mentioned.
As a conventionally known method, there is a method using a polymer having enhanced affinity with carbon black and silica (for example, Patent Document 1). According to Patent Document 1, the exothermic property of the rubber composition can be lowered by increasing the affinity between the filler and the rubber component. Thereby, a tire with low hysteresis loss can be obtained. However, as the fuel efficiency of automobiles has further improved, further improvements in low heat generation have been desired for tires.
In addition, other methods are known in which the kneading time is increased, but there is a limit to the reduction in heat generation.

Special table 2003-514079 gazette JP 2011-38945 A

A. Papon et al. “Low-Field NMR Investigation of Nanocomposites: Polymer Dynamics and Network Effects” Macromolecules 44, 913-922 (2011).

An object of the present invention is to provide a polymer composition, a rubber composition, a cross-linked rubber composition, and a tire manufacturing method that have good low heat build-up .

The method for producing a polymer composition of the present invention is a method for producing an unvulcanized polymer composition comprising 2 parts by mass or more of silica with respect to 100 parts by mass of a polymer component,
A polymer composition is produced by adding silica having a water content of 0.1 to 20% by weight to the polymerization catalyst composition used for the polymerization reaction of the monomer constituting the polymer component,
The polymer component is either a polymer of only a conjugated diene compound, or a polymer of a conjugated diene compound and a non-conjugated olefin,
The polymerization catalyst composition has the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different, and Y is from group 1 of the periodic table When it is a selected metal, a is 1 and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from group 13 of the periodic table, a, b and c are 1). And a third element containing 2 parts by mass or more of silica with respect to 100 parts by mass of the polymer component, and then a rare earth element compound or the rare earth element Adding a first element which is a rare earth element-containing compound including a reaction product of a compound and a Lewis base,
The proportion y of stationary phase hydrogen nuclei in the hydrogen nuclei in the polymer composition is
y ≧ 0.02x + 0.2
It is characterized by satisfying the formula of (x is the compounding amount (part by mass) of silica, and y is the ratio of stationary phase hydrogen nuclei in hydrogen nuclei).
Stationary phase hydrogen nuclei are hydrogen nuclei in polymer compositions that are in a state of reduced mobility and fluidity due to direct or indirect bonding to silica, either covalently or non-covalently. It shall refer to the nucleus.
The ratio of stationary phase hydrogen nuclei can be calculated using a magic sandwich echo (Magic Sandwich Echo, MSE) method. Details of the MSE method are described in Non-Patent Document 1.
By configuring the ratio of stationary phase hydrogen to a certain amount or more with respect to the amount of silica, it is possible to achieve better low heat generation as compared with the amount of silica. That is, it is possible to provide a polymer composition in which silica is more highly dispersed in the polymer component.

  In the polymer composition, the polymer component is preferably unmodified. By making the polymer component unmodified, the modification step can be omitted. The polymer composition of the present invention has an advantage that silica is obtained in a highly dispersed state without undergoing a modification treatment of the polymer component.

  It is preferable that the compounding quantity of a silane coupling agent is less than 5 mass parts with respect to 100 mass parts of said polymers. Thereby, the usage-amount of a silane coupling agent can be reduced or a mixing | blending can be abbreviate | omitted and it is possible to reduce manufacturing cost. The polymer composition of the present invention is advantageous in that silica can be obtained in a highly dispersed state even if the amount of the silane coupling agent is reduced or the mixing and kneading of the silane coupling agent is omitted. .

Method for producing a rubber composition of the present invention is characterized Rukoto using the polymer composition. The method for producing a crosslinked rubber composition of the present invention is characterized in that the rubber composition is crosslinked. A method of manufacturing a tire according to the invention is characterized in that Ru using the cross-linked rubber composition. Thereby, it becomes possible to obtain a rubber composition, a crosslinked rubber composition, and a tire excellent in low heat generation.

According to the present invention, it is possible to provide a polymer composition, a rubber composition, a vulcanized rubber composition, and a method for producing a tire that have good low heat build-up .

It is the schematic of the signal of a pulse NMR method. It is the schematic of the signal of a spin echo method. It is the schematic of the signal of a magic sandwich echo method. It is a correlation diagram (graph) which shows the relationship between the addition amount of a silica, and the ratio of the stationary phase hydrogen nucleus in a hydrogen nucleus.

Hereinafter, the polymer composition of the present invention will be described.
(Polymer component)
Polymer component constituting the polymer composition of the present invention, a conjugated diene compound alone, or a polymer of a conjugated diene compound and a non-conjugated olefin. That is, it is a conjugated diene polymer or a copolymer of a conjugated diene compound and a non-conjugated olefin , and hereinafter these are collectively referred to as a conjugated diene polymer.

  The conjugated diene compound used as the monomer preferably has 4 to 8 carbon atoms, and 1,3-butadiene and isoprene are particularly preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  On the other hand, the non-conjugated olefin used as the monomer is an olefin other than the conjugated diene compound, and is preferably an acyclic olefin. Moreover, it is preferable that carbon number of this nonconjugated olefin is 2-8, ethylene, propylene, and 1-butene are more preferable, and ethylene is especially preferable. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  When the polymer is a copolymer, the copolymer may be any of alternating copolymer, periodic copolymer, random copolymer, block copolymer, graft copolymer, taper copolymer, etc. Although not particularly limited, block copolymers and taper copolymers are preferred.

The number average molecular weight (Mn) of the polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100,000 to 400,000, more preferably 150,000 to 300,000. When the number average molecular weight (Mn) is 150,000 or more, a crosslinked polymer composition having improved durability (destructive properties and wear resistance) can be obtained. Moreover, it can prevent that workability falls that the said number average molecular weight (Mn) is 300,000 or less. On the other hand, when the number average molecular weight (Mn) is within the more preferable range, it is further advantageous in terms of both durability and workability.
Here, the number average molecular weight (Mn) is determined as a polystyrene-converted average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) at a measurement temperature of 140 ° C.

  The molecular weight distribution (Mw / Mn) represented by the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer is not particularly limited and may be appropriately selected according to the purpose. 4.0 or less is preferable and 3.0 or less is more preferable. When the molecular weight distribution (Mw / Mn) is 4.0 or less, physical properties can be made uniform. On the other hand, if it is within the more preferable range, it is advantageous also in terms of low heat generation. Here, the molecular weight distribution (Mw / Mn) is a weight average molecular weight (Mw) and a number average molecular weight as a polystyrene-converted average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) at a measurement temperature of 140 ° C. (Mn) is calculated and calculated from the calculated weight average molecular weight (Mw) and number average molecular weight (Mn).

There is no restriction | limiting in particular as a gel fraction in the said polymer, Although it can select suitably according to the objective, 40% or less is preferable and 20% or less is more preferable.
When the gel fraction in the polymer is 40% or less, a crosslinked polymer composition having improved durability (breakage resistance and wear resistance) can be obtained.
In addition, the polymer whose gel fraction in a polymer is 40% or less is low temperature (-50-100 degreeC) using the 1st, 2nd, or 3rd polymerization catalyst composition mentioned later, for example. , By polymerization for a predetermined time (30 minutes to 2 days).

<Microstructure of the conjugated diene compound-derived portion>
-Cis-1,4 binding amount-
The cis-1,4 bond amount of the conjugated diene compound-derived portion of the polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 90% or more, more preferably 95% or more, 98% or more is particularly preferable.
When the amount of cis-1,4 bonds is 90% or more, sufficient elongation crystallinity can be expressed.
On the other hand, when the amount of cis-1,4 bonds is within the more preferable range or the particularly preferable range, it is further advantageous in terms of improvement in durability due to stretched crystallinity.

-Trans-1,4 binding amount-
There is no restriction | limiting in particular as trans-1,4 bond amount of the conjugated diene compound origin part of the said polymer, Although it can select suitably according to the objective, 10% or less is preferable and 5% or less is more preferable.
When the amount of the trans-1,4 bond is 10% or less, sufficient elongation crystallinity can be expressed.
On the other hand, when the amount of the trans-1,4 bond is within the more preferable range, it is further advantageous in terms of improvement in durability due to stretched crystallinity.

−3,4-vinyl bond amount−
There is no restriction | limiting in particular as the 3, 4- vinyl bond amount of the conjugated diene compound origin part of the said polymer, Although it can select suitably according to the objective, 5% or less is preferable and 2% or less is more preferable.
When the 3,4-vinyl bond amount is 5% or less, sufficient elongation crystallinity can be expressed.
On the other hand, when the amount of 3,4-vinyl bond is within the more preferable range, it is further advantageous in terms of improvement in durability due to stretched crystallinity.

<Characteristics of polymer component>
The polymer component constituting the polymer composition of the present invention is preferably unmodified. In the conventional silica-containing rubber composition, the rubber component is an amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl group, epoxy. Modified with a polar group-containing monomer such as a group, oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group, alkoxysilyl group, It has been common to increase the affinity with silica by tin modification and to increase the dispersibility of silica. The polymer composition of the present invention can highly disperse the blended silica without modifying the polymer component. In the production of the polymer composition of the present invention, there is an advantage that a polymer component modification treatment step is not required.

(Polymer composition)
The polymer composition of the present invention contains 2 parts by mass or more of silica with respect to 100 parts by mass of the polymer component.

<Silica>
The blended silica is preferably 2 parts by mass or more, more preferably 10 parts by mass or more, with respect to 100 parts by mass of the polymer component.
The term “silica” specifically means not only narrowly defined silicon dioxide (generally represented by SiO ₂ ), but a silicate-based filler, specifically, anhydrous silica. In addition to acids, silicates such as hydrous silicate, calcium silicate, and aluminum silicate are included. In addition, precipitation method silica, gel method silica, dry silica, colloidal silica and the like are included regardless of the aggregation state of silica. Moreover, the silica manufactured by any manufacturing method is included, and both a wet method and a dry method are included. Of these, wet silica having excellent wear resistance is preferred. The BET of silica is not particularly limited, and includes, for example, silica in the range of 10 to 1000 m ² / g. Examples of such silica include “Nip Seal AQ” manufactured by Tosoh Silica Co., Ltd. and BET 205 m ² / g.
In addition, it is preferable that a part or all of the silica blended in the polymer composition of the present invention is used as a part of the third element of the polymerization catalyst composition of the polymer component described later.

<Silane coupling agent>
The blending amount of the silane coupling agent in the polymer composition of the present invention is preferably less than 5 parts by mass and more preferably less than 4 parts by mass with respect to 100 parts by mass of the polymer component. Most preferably, it is desirable that the silane coupling agent is not included. With such a configuration, the kneading operation of the silane coupling agent can be omitted.
In addition, when using a silane coupling agent, the kind will not be specifically limited if it is normally used in the rubber industry, but specifically, bis (3-triethoxysilylpropyl) tetrasulfide, γ-mercapto Propyltriethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are preferred.

<Measurement method of the proportion of stationary phase hydrogen nuclei>
The polymer composition of the present invention is characterized in that the proportion y of stationary phase hydrogen nuclei in the hydrogen nuclei in an unvulcanized state satisfies the following formula.
y ≧ 0.02x + 0.2
(X is the compounding amount of silica (parts by mass), y is the ratio of stationary phase hydrogen nuclei in hydrogen nuclei)
The term “stationary phase hydrogen nucleus” as used herein refers to a state in which the mobility / fluidity of hydrogen in the rubber composition is lowered by directly or indirectly binding to silica through covalent bonding or non-covalent bonding. Of hydrogen.
More preferably, y satisfies the following formula:
y ≧ 0.02x + 0.3
Further, it is more preferable to satisfy the following formula.
y ≧ 0.02x + 0.5
When y satisfies the above-mentioned more preferable formula and the more preferable formula, it is possible to obtain a rubber composition having an excellent low heat generation property.

  The ratio of stationary phase hydrogen nuclei in the hydrogen nuclei can be calculated using pulsed NMR, more preferably spin echo method or Magic Sandwich Echo (MSE) method modified from this.

（式中、Ｔ_２Ｍは緩和時間の短い成分の緩和時間、Ｔ_２Ｌは緩和時間の長い成分の緩和時間、Ａ_２Ｍは緩和時間の短い成分のｔ＝０時の強度、Ａ_２Ｌは緩和時間の長い成分のｔ＝０時の強度、ｔは観測時間である。）
上記式において、Ｔ_２Ｍが固定相水素核の緩和時間、Ｔ_２Ｌが流動相水素核の緩和時間であり、これらの緩和時間成分を解析することで、全水素核中の固定相水素核の割合を算出することが可能となる。
ここで、Ｔ_２Ｍ成分、つまり、固定相水素核の強度は

で表され、
Ｔ_２Ｌ成分、つまり、流動相水素核の強度は

で表される。 The fixed NMR in all hydrogen nuclei is obtained from the free induction decay (FID) curve of the macroscopic magnetic field after the pulse applied in one direction to the hydrogen nuclei by the pulse NMR method conventionally used to investigate the state of the polymer. It is possible to calculate the proportion of phase hydrogen nuclei. That is, this is a method of calculating a T _2L component (so-called soft component) having two relaxation times and a T _2M component (so-called hard component) from the FID curve by the following formula (1) indicating the signal intensity F (Patent Document 1). ).

(In the formula, T _2M is a relaxation time of a component having a short relaxation time, T _2L is a relaxation time of a component having a long relaxation time, A _2M is a strength of a component having a short relaxation time at t = 0, and A _2L is a relaxation time of the component. (The intensity of the long component at t = 0, t is the observation time.)
In the above equation, T _2M is the relaxation time of stationary phase hydrogen nuclei, and T _2L is the relaxation time of fluid phase hydrogen nuclei. By analyzing these relaxation time components, the ratio of stationary phase hydrogen nuclei in all hydrogen nuclei Can be calculated.
Here, the strength of the T _2M component, that is, the stationary phase hydrogen nucleus is

Represented by
T _2L component, that is, the strength of fluid phase hydrogen nucleus is

It is represented by

即ち、水素核中の固定相水素核の占める割合ｙ＝Ａ_２Ｍ／（Ａ_２Ｍ＋Ａ_２Ｌ）となる。
ただし、図１に示すように、パルスＮＭＲ法によると、ＦＩＤ初期の信号にノイズが発生しやすく（図１中破線部分）、正確な算出が困難となりやすい。なお、図１中の「軟」は運動性の高いゴム部分の流動相水素核の成分を示し、「硬」はシリカ周りに拘束された運動性の低い固定相水素核の成分を示す。 By applying the signal obtained by the pulse NMR method for the polymer composition to the above formula (1), the ratio of both components can be determined as follows.

That is, the ratio of the stationary phase hydrogen nuclei in the hydrogen nuclei is y = A _2M / (A _2M + A _2L ).
However, as shown in FIG. 1, according to the pulse NMR method, noise is likely to occur in the initial signal of the FID (the broken line portion in FIG. 1), and accurate calculation is likely to be difficult. In FIG. 1, “soft” indicates a component of a fluid phase hydrogen nucleus of a rubber portion having high mobility, and “hard” indicates a component of a stationary phase hydrogen nucleus of low mobility restricted around silica.

  In order to eliminate noise at the initial stage of FID, the spin (Hahn) echo method shown in FIG. 2 can be preferably used. As shown in FIG. 2, the spin echo method is a method in which a pulse of 180 ° is further applied when a 90 ° pulse is applied to the hydrogen nucleus and the attenuation proceeds. As a result, it is possible to analyze the peak curve, and there is an advantage that the initial noise is eliminated. However, as shown as “difference” in FIG. 2, according to the spin echo method, the signal at the peak time is lower than that of the conventional pulse induction method, and the signal of the hydrogen nucleus in the stationary phase is reduced. It tends to be difficult to obtain sufficiently.

  It is further preferable to use the magic sandwich echo (MSE) method in order to obtain a sufficient signal of the stationary phase hydrogen nucleus. As shown in FIG. 3, the MSE method is a method of applying a plurality of 90 ° pulses successively after the 180 ° pulse of the spin echo method (Non-patent Document 1). In FIG. 3, “soft” indicates a component of a fluid phase hydrogen nucleus of a rubber portion having high mobility, and “hard” indicates a component of a stationary phase hydrogen nucleus of low mobility confined around silica. According to this method, there is an advantage that accurate calculation is possible even for stationary phase hydrogen nuclei, that is, hard components, without the reduction in peak intensity seen in the spin echo method.

(Method for producing polymer composition)
The polymer is not modified, preferably no silica coupling agent is used, and as described above, the proportion y of the stationary phase hydrogen nuclei in the hydrogen nuclei of the polymer composition is constant with respect to the amount of silica. In order to achieve the above , the following manufacturing method is used . That is, by adding silica to the polymerization catalyst composition used for the polymerization reaction of the monomer constituting the target polymer, a structure in which silica is highly dispersed in the produced polymer is obtained.
Although the polymer used for the polymer composition of this invention is not specifically limited, In the following manufacturing methods, the method to manufacture a conjugated diene type polymer is demonstrated. However, the manufacturing method described in detail below is merely an example. The conjugated diene polymer can be produced by polymerizing a conjugated diene compound and / or a non-conjugated olefin in the presence of a polymerization catalyst composition.

<Polymerization catalyst composition>
The polymerization catalyst composition used in the above method for producing a conjugated diene polymer can be obtained by combining the following first element, second element and third element.

<< First Element >>
The first element constituting the polymerization catalyst composition is a rare earth element-containing compound. The first element includes a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base as the rare earth element-containing compound. Here, the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base preferably do not have a bond between the rare earth element and carbon. When the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. A 1st element may be used individually by 1 type, and may be used in combination of 2 or more type.
As the rare earth element-containing compound, the following rare earth element-containing compounds can be preferably used.

<<< Rare earth element-containing compound >>>
The rare earth element-containing compound may have the following structure. Preferably, the rare earth metal is a divalent or trivalent salt or complex compound, and the rare earth element-containing compound contains one or more ligands selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is preferably the following general formula (i) or (ii):
MX ₂ · Lw (i)
MX ₃ · Lw (ii)
(In the formula, M represents a lanthanoid element, scandium or yttrium, and each X independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue, A carboxylic acid residue, a thiocarboxylic acid residue, a phosphorus compound residue, an unsubstituted or substituted cyclopentadienyl, or an unsubstituted or substituted indenyl; L represents a Lewis base; Can be included).

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element-containing compound include a hydrogen atom; methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert -Aliphatic alkoxy group such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6 -Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group, thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, Aliphatic thiolate groups such as thiosec-butoxy group and thiotert-butoxy group; Phenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2 Arylthiolate groups such as -tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, 2,4,6-triisopropylthiophenoxy; dimethylamide, diethylamide, diisopropyl Aliphatic amide group such as amide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert- Butyl-6-isopropylphenylamide group, 2-tert Arylamide groups such as butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilylamides such as bistrimethylsilylamide group Groups: silyl groups such as trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; fluorine atom, chlorine atom, bromine atom, iodine And halogen atoms such as atoms. Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone residues; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [trade name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as: dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, dilauryl phosphate Dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Residues of phosphonic acid esters such as mono-1-methylheptyl phosphonate and mono-p-nonylphenyl phosphonate; dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the Lewis base that reacts with the rare earth element compound in the first element include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. . Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (I) and (II), when w is 2 or 3), the Lewis bases L are the same or different. May be.

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）： <<< preferred rare earth element-containing compound >>>
As the rare earth element-containing compound, the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ'は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体より選択される少なくとも１種類の錯体を含むことが好ましい。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3). It is preferable that the complex is included.

Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

  The central metal M in the general formulas (I) and (II) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Suitable examples of the central metal M include samarium, neodymium, praseodymium, gadolinium, cerium, holmium, scandium, and yttrium.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. It is a group. Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  The metallocene complex represented by the general formulas (I) and (II) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Moreover, the metallocene complex represented by the general formula (I) and the formula (II) may exist as a monomer, or may exist as a dimer or a higher multimer.

（式中、Ｘ''はハライドを示す。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩（例えばカリウム塩やリチウム塩）及びシリルの塩（例えばカリウム塩やリチウム塩）と反応させることで得ることができる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンを用いればよい。以下に、一般式（ＩＩ）で表されるメタロセン錯体を得るための反応例を示す。 The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

(In the formula, X ″ represents a halide.)
The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, a scandium trishalide, or a yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

（式中、Ｘ''はハライドを示す。）

(In the formula, X ″ represents a halide.)

  The structure of the metallocene complex represented by general formula (I) or formula (II) is preferably determined by X-ray structural analysis.

<<< other suitable rare earth element-containing compound >>>
The rare earth element-containing compound has the following general formula (A):

R _a MX _b QY _b (A) (wherein R independently represents unsubstituted or substituted indenyl, R is coordinated to M, and M represents a lanthanoid element, scandium or yttrium) X is independently a hydrocarbon group having 1 to 20 carbon atoms, X is μ-coordinated to M and Q, Q is a Group 13 element of the Periodic Table, and Y is independently Or a metallocene compound represented by the formula (1): a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, wherein Y is coordinated to Q, and a and b are 2. Rare earth element-containing compounds).

（式中、Ｍ^１は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^Ａ及びＲ^Ｂは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^Ａ及びＲ^Ｂは、Ｍ^１及びＡｌにμ配位しており、Ｒ^Ｃ及びＲ^Ｄは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）で表されるメタロセン系化合物が挙げられる。 In a preferred example of the metallocene compound, the following general formula (XV):

(In the formula, M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^A and R ^B each independently have 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene compounds represented by

  Hereinafter, the metallocene compound will be described in detail. The metallocene compound represented by the general formula (A) reduces or eliminates the amount of alkylaluminum used at the time of copolymer synthesis, for example, by using a catalyst that is previously combined with an aluminum catalyst. It becomes possible. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene compound of the above formula (A) is used, by adding about 5 equivalents of alkylaluminum, Excellent catalytic action is exhibited.

  In the metallocene compound, the metal M in the formula (A) has the same meaning as the central metal M in the general formulas (I) and (II).

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.

  In the above formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the above formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, it is synonymous with X of Formula (A).

In the above formula (XV), the metal M ¹ has the same meaning as the central metal M in the general formulas (I) and (II).

In the above formula (XV), Cp ^R is synonymous with Cp ^R represented by the above general formula (I) and formula (II), and the two Cp ^R may be the same or different from each other.

In the above formula (XV), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R ^B are μ-coordinated to M ¹ and Al. Here, as a C1-C20 hydrocarbon group, it is synonymous with X of Formula (A). Note that the μ coordination is a coordination mode having a crosslinked structure.

In the above formula (XV), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, it is synonymous with X of Formula (A).

（式中、Ｍ^２は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Ｒは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^Ｅ〜Ｒ^Ｊは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^ＫＲ^ＬＲ^Ｍで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系化合物の構造は、^１Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。 The metallocene compound represented by the above formula (XV) is, for example, in a solvent, represented by the following general formula (XVI):

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently has 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3, and a metallocene complex represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. Note that the structure of the metallocene compound is preferably determined by ¹ H-NMR or X-ray structural analysis.

In the metallocene complex represented by the above formula (XVI), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the above formula (XV). In the above formula (XVI), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (XV).

The metallocene complex represented by the above formula (XVI) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. In addition, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the synthesis of the catalyst becomes easy. Furthermore, a methyl group is preferable as the alkyl group.

  The metallocene complex represented by the above formula (XVI) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  In addition, the metallocene complex represented by the above formula (XVI) may exist as a monomer, or may exist as a dimer or a higher multimer.

On the other hand, the organoaluminum compound used to produce the metallocene compound is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent hydrocarbon having 1 to 20 carbon atoms. A group or a hydrogen atom, R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from the above R ^K or R ^L. The monovalent hydrocarbon group having 1 to 20 carbon atoms has the same meaning as X in the formula (A).

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. The amount of the organoaluminum compound used for the production of the metallocene compound is preferably 1 to 50 times mol, more preferably about 10 times mol to the metallocene complex.

<< Second Element >>
The second element constituting the polymerization catalyst composition is the following general formula (X)
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different, and Y is from group 1 of the periodic table When it is a selected metal, a is 1 and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1).

In addition, the second element has the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
(Wherein, ^{R 1} and ^{R 2} is a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, ^{R 3} is a hydrocarbon group having 1 to 10 carbon atoms, provided ^that, R 1, ^{R 2} and ^{R 3} Are preferably the same or different from each other). Examples of the organoaluminum compound represented by the general formula (Xa) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum. , Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diiso hydrogenated Hexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Um dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the second element described above can be used singly or in combination of two or more. In addition, it is preferable that the compounding quantity of the 2nd element in a polymerization catalyst composition is 1-50 times mol with respect to the said 1st element, and it is still more preferable that it is about 10 times mol.

<< Third element >>
The 3rd element which comprises said polymerization catalyst composition contains a silica. As described above, the amount of silica is 2 parts by mass or more per 100 parts by mass of the polymer component in the polymer composition to be produced.
In the production of the polymerization catalyst composition described above, the silica preferably contains moisture, and does not require firing of the silica.

<< Preparation process of polymerization catalyst composition >>
The polymerization catalyst composition is obtained by mixing and aging the second element and the third element, and then adding and reacting the first element. First, by mixing and aging the second element and the third element in a solvent, the moisture of the second element and the third element reacts to form a negatively charged complex (anionic complex). . This reaction is described in detail by S. Pasynkiewicz in Polyhedron, Vol. 9, 429-453 (1990), for example, that methylaluminoxane is produced by the reaction of alkylaluminum and water. It is supported from. As a result, it is assumed that the anion complex containing the second element is present in the vicinity of the silica of the third element as if a film is formed.
Under this circumstance, by adding the rare earth element-containing compound, which is the first element, to cause the reaction, the rare earth element cationic compound derived from the first element and the second element, and the reaction between the second element and the third element are derived. Thus, a silica-containing anion complex is produced in the reaction system.
The rare earth element of the rare earth element-containing compound of the first element is usually coordinated by three ligands, but depending on conditions, one or more of the ligands are separated in the presence of an anion to be cationized. It has the characteristic. Therefore, by reacting the anion complex formed by reacting the second element and the third element with the first element, the first element is cationized, and then the anion complex is bound to the generated cation. It is easy to be in a state.
Here, in the catalyst composition having a rare earth element cationic compound, when a metal such as aluminum (here, Y) is adjacent to the rare earth element, the active center of the catalyst is not the rare earth element, but the adjacent metal element Y side. (Y. Matsura et al., “Polymerization via the the stigmum and the clotted cermets”). , The Kinki Chemical Society, Japan, 2011). In the case of the polymerization catalyst composition, the active center of the polymerization reaction is transferred to the adjacent metal element Y instead of the rare earth element, and a polymer as the target product is produced in Y.
In the polymerization catalyst composition described above, since the rare earth element is present in a state adjacent to the metal element Y existing in a film form on the silica particles, the active center can be transferred onto the silica particles. As a result, the polymerization reaction produces a polymer very close to the silica. Some of the polymer enters the porous silica and may be integrated with the silica particles.
Thus, in the polymerization catalyst composition described above, the metal element Y derived from the second element, the silica derived from the third element, and the polymer are close to or integrated with each other, whereby silica is contained in the produced polymer. Can exist in a highly dispersed state.

  Usually, in a polymerization catalyst composition containing a rare earth element-containing compound, in order to increase the efficiency of the polymerization reaction, the amount of the rare earth element compound is increased, but since the rare earth element compound is expensive, a large amount There was a problem that it was difficult to use. However, when the above polymerization catalyst composition is used, the efficiency of the polymerization reaction depends on the blending amounts of silica and metal element Y, not the rare earth element compound. It can be said that the increase in the manufacturing cost by increasing these compounding amounts is relatively low.

In addition, although there exists a problem that a 1st element is easy to deactivate by presence of water, even if it coexists with the said anion complex, a 1st element is hard to deactivate. Therefore, the silica as the third element does not need to be anhydrous by calcination or the like. Since the steps such as firing can be omitted, the manufacturing cost can be reduced and the manufacturing process can be made more efficient. Rather, for the promotion of the polymerization reaction, the third element is preferably to contain a certain amount or more of water, the water content is 0.1 to 20 wt%, the preferred water content from 0.5 to 10 weight %.

(Manufacturing process of conjugated diene polymer)
In describing the production process of the conjugated diene polymer, the production process of polybutadiene will be exemplified below. The production of polybutadiene using the polymerization catalyst composition includes at least a polymerization step, and further includes a coupling step, a washing step, and other steps that are appropriately selected as necessary.

<Polymerization process>
The polymerization step is a step of polymerizing a butadiene monomer.
In the polymerization step, 1,3-butadiene, which is a monomer, can be polymerized in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst composition is used. it can.

  As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  The said polymerization process is comprised by adding the monomer made to superpose | polymerize in the polymerization catalyst composition prepared previously.

  In the polymerization step, the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, isopropanol or the like.

  In the polymerization step, the polymerization reaction of 1,3-butadiene is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction takes in 1,3-butadiene fully in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. The reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, but can be appropriately selected depending on conditions such as the type of catalyst and the polymerization temperature.

<Washing process>
The washing step is a step of washing the silica-containing polymer obtained in the polymerization step. In addition, there is no restriction | limiting in particular as a medium used for washing | cleaning, According to the objective, it can select suitably, For example, methanol, ethanol, isopropanol etc. are mentioned. Further, an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) may be added to these solvents. The amount of the acid to be added is preferably 15 mol% or less with respect to the solvent. Above this, the acid remains in the silica-containing polymer, which may adversely affect the reaction during kneading and vulcanization.

(Rubber composition)
The rubber composition of the present invention contains at least the above polymer composition, and further contains other polymer components, fillers, cross-linking agents, and other components as necessary.

<Other polymer components>
The rubber composition of the present invention may contain other polymer components. There is no restriction | limiting in particular as another polymer, According to the objective, it can select suitably, For example, butadiene (BR), styrene butadiene (SBR), acrylonitrile-butadiene (NBR), chloroprene rubber, ethylene-propylene rubber Examples thereof include rubber components such as (EPM), ethylene-propylene-nonconjugated diene rubber (EPDM), polysulfide rubber, silicone rubber, fluorine rubber, and urethane rubber. These may be used individually by 1 type and may use 2 or more types together.

<Fillers other than silica>
The filler other than silica is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include carbon black and inorganic filler. At least one selected from carbon black and inorganic filler can be used. Is preferred. Here, it is more preferable that the polymer composition contains carbon black. In addition, the said filler is mix | blended with a polymer composition in order to improve reinforcement property etc.

There is no restriction | limiting in particular as a compounding quantity (content) of the filler added after a polymerization reaction, Although it can select suitably according to the objective, 10 mass parts-100 mass parts are with respect to 100 mass parts of polymer components. Preferably, 20 parts by weight to 80 parts by weight is more preferable, and 30 parts by weight to 60 parts by weight is particularly preferable.
When the blending amount of the filler is 10 parts by mass or more, the effect of adding the filler is seen, and when it is 100 parts by mass or less, the synthetic rubber component can be sufficiently mixed with the filler. The performance as a composition can be improved.
On the other hand, when the blending amount of the filler is within the more preferable range or the particularly preferable range, it is more advantageous in terms of the balance between workability and low heat buildup / durability.

<< carbon black >>
There is no restriction | limiting in particular as said carbon black, According to the objective, it can select suitably, For example, FEF, GPF, SRF, HAF, N339, IISAF, ISAF, SAF etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Nitrogen adsorption specific surface area of the carbon black: The _(N 2 SA, JIS K 6217-2 is measured according to 2001) is not particularly limited and may be appropriately selected depending on the intended purpose, ^{20 m} 2 / 150 m ² / g are ^preferred, 35m ² / ^g~145m 2 / g is more preferable.
When the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 20 m ² / g or more, the durability of the obtained rubber composition is prevented from deteriorating and sufficient crack growth resistance is obtained. When it is 100 m ² / g or less, low heat build-up can be improved, and workability can be improved.
There is no restriction | limiting in particular as content of carbon black with respect to 100 mass parts of said polymer components, Although it can select suitably according to the objective, 10 mass parts-100 mass parts are preferable, and 10 mass parts-70 mass parts are preferable. Is more preferable, and 20 to 60 parts by mass is particularly preferable.
When the content of the carbon black is 10 parts by mass or more, it is possible to prevent the reinforcing property from being insufficient and the fracture resistance to be deteriorated, and when it is 100 parts by mass or less, the workability and the low exothermic property. Can be prevented from deteriorating.
On the other hand, when the content of the carbon black is within the more preferable range or the particularly preferable range, it is more advantageous in terms of balance of performances.

<< Inorganic filler >>
The inorganic filler is not particularly limited except for silica, and can be appropriately selected according to the purpose. For example, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, carbonic acid Examples include calcium, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, potassium titanate, and barium sulfate. These may be used individually by 1 type and may use 2 or more types together.

<Crosslinking agent>
There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, a sulfur type crosslinking agent, an organic peroxide type crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, sulfur A compound type crosslinking agent, an oxime-nitrosamine type crosslinking agent, etc. are mentioned, Among these, a sulfur type crosslinking agent is more preferable.

  There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of synthetic rubber components. When the content of the crosslinking agent is 0.1 parts by mass or more, crosslinking can proceed, and when the content is 20 parts by mass or less, a part of the crosslinking agent prevents crosslinking from proceeding during kneading. Or the physical properties of the vulcanizate can be prevented from being impaired.

<Other ingredients>
In addition, it is also possible to use a vulcanization accelerator in combination, and examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, Dithiocarbamate and xanthate compounds can be used.
If necessary, softeners, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, scorch inhibitors, UV inhibitors, antistatic agents Known agents such as a colorant, an anti-coloring agent, and other compounding agents can be used depending on the purpose of use.

(Crosslinked rubber composition)
The rubber composition of the present invention may be cross-linked and used as a cross-linked rubber composition.
The crosslinked rubber composition is not particularly limited as long as it is obtained by crosslinking the rubber composition of the present invention, and can be appropriately selected according to the purpose.
The crosslinking conditions are not particularly limited and may be appropriately selected depending on the intended purpose. However, a temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes are preferable.

(tire)
The tire of the present invention is not particularly limited as long as it has the crosslinked rubber composition of the present invention, and can be appropriately selected according to the purpose.
The application site in the tire of the crosslinked rubber composition of the present invention is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include treads, base treads, sidewalls, side reinforcing rubbers, and bead fillers. It is done.
Among these, it is advantageous in terms of durability that the application site is a tread.
As a method for manufacturing the tire, a conventional method can be used. For example, members used in normal tire production such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber and / or cord are sequentially laminated on a tire molding drum, and the drum is removed to obtain a green tire. Then, a desired tire (for example, a pneumatic tire) can be manufactured by heating and vulcanizing the green tire according to a conventional method.

(Applications other than tires)
Besides the tire application, the crosslinked rubber composition of the present invention can be used for vibration-proof rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, various hoses and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Example 1: Production method of polymer composition A)
In a glove box under a nitrogen atmosphere, 3 g of silica (trade name: nip seal AQ, water content of 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.), 40.0 g of toluene, Trimethylaluminum 10.0 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 10.0 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 68 mg (100 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out from the glove box, and 530.0 g of a toluene solution containing 80 g (1.48 mol) of 1,3-butadiene was added, followed by polymerization at 50 ° C. for 180 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum-dried at 70 ° C. to obtain a polymer composition A. The yield of the obtained polymer composition A was 77 g.

(Example 2: Production method of polymer composition B)
In a glove box under a nitrogen atmosphere, 4 g of silica (trade name: Nipseal AQ, water content 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, 55.0 g of normal hexane Then, 12.0 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 20.0 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 68 mg (100 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Then, after taking out the reactor from the glove box and adding 350.0 g of normal hexane solution containing 80 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 65 ° C. for 180 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum dried at 70 ° C. to obtain a polymer composition B. The yield of the obtained polymer composition was 82 g.

(Example 3: Production method of polymer composition C)
In a glove box under a nitrogen atmosphere, 4 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Corporation) in a 1 L pressure-resistant glass reactor, 25.0 g of normal hexane Then, 12.8 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 3.2 mmol of diisobutylaluminum hydride (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 43 mg (64 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Then, after taking out the reactor from the glove box and adding 400.0 g of normal hexane solution containing 80 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 65 ° C. for 300 minutes. After the polymerization, 2 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by weight of isopropanol solution was added to stop the reaction, and a large amount of methanol was separated. The polymer composition C was obtained by vacuum drying at 70 ° C. The yield of the obtained polymer composition C was 74 g.

(Example 4: Production method of polymer composition D)
In a glove box under a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 50 0.0 g, 20.0 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 20.0 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 68 mg (100 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out from the glove box, and after adding 470.0 g of a normal hexane solution containing 100.0 g (1.85 mol) of 1,3-butadiene, polymerization was carried out at 65 ° C. for 250 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum dried at 70 ° C. to obtain a polymer composition. The yield of the obtained polymer composition D was 88.0 g.

(Example 5: Production method of polymer composition E)
In a glove box under a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 50 0.0 g, 12.0 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 20.0 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 68 mg (100 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Then, after taking out the reactor from the glove box and adding 350.0 g of normal hexane solution containing 80.0 g (1.85 mol) of 1,3-butadiene, polymerization was carried out at 65 ° C. for 180 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum dried at 70 ° C. to obtain a polymer composition E. The yield of the obtained polymer composition E was 70.0 g.

(Example 6: Production method of polymer composition F)
In a glove box in a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, normal hexane 65 0.0 g, trimethylaluminum 16.0 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 2.6 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out from the glove box, and 340.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene was added, followed by polymerization at 80 ° C. for 240 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum dried at 70 ° C. to obtain a polymer composition F. The yield of the obtained polymer composition F was 66.0 g.

(Example 7: Production method of polymer composition G)
In a glove box under a nitrogen atmosphere, 8.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 80 0.06 g, trimethylaluminum 16.8 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 16.8 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out of the glove box, and after adding 320.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 80 ° C. for 240 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum dried at 70 ° C. to obtain a polymer composition G. The yield of the obtained polymer composition G was 83.0 g.

(Example 8: Production method of polymer composition H)
In a glove box under a nitrogen atmosphere, 8.0 g of silica (trade name: Nipseal AQ, water content of 5.5% by weight calculated by the weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure glass reactor, normal hexane 80 0.0 g, 19.2 mmol of trimethylaluminum (manufactured by Tosoh Finechem Co., Ltd.) and 19.2 mmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Then, after taking out the reactor from the glove box and adding 320.0 g of normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene, polymerization was performed at 80 ° C. for 200 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum dried at 70 ° C. to obtain a polymer composition H. The yield of the obtained polymer composition H was 68.0 g.

(Example 9: Production method of polymer composition I)
In a glove box in a nitrogen atmosphere, 5.0 g of silica (trade name: Nipseal AQ, water content 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) in a 1 L pressure-resistant glass reactor, normal hexane 65 0.0 g, trimethylaluminum 16.0 mmol (manufactured by Tosoh Finechem Co., Ltd.) and triisobutylaluminum 3.2 mmol (manufactured by Tosoh Finechem Co., Ltd.) were charged and mixed and aged at room temperature for 30 minutes. Next, 22 mg (32 μmol) of bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] was charged and aged at room temperature for 60 minutes. Thereafter, the reactor was taken out from the glove box, and 340.0 g of a normal hexane solution containing 80.0 g (1.48 mol) of 1,3-butadiene was added, followed by polymerization at 80 ° C. for 90 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 wt% isopropanol solution was added to stop the reaction, and the polymer composition was further added with a large amount of methanol. The product was separated and vacuum dried at 70 ° C. to obtain a polymer composition I. The yield of the obtained polymer composition I was 27.0 g.

(Comparative Example 1)
As Comparative Example 1, polybutadiene rubber (UBEPOL BR 150, hereinafter referred to as “150 L butadiene”) manufactured by Ube Industries, Ltd. was used.

(Comparative Example 2: Composition J)
As Comparative Example 2, 5 parts by mass of silica (trade name: nip seal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) was added to 100 parts by mass of 150 L butadiene. The mixture was kneaded at 110 ° C. for 3 minutes with a mixer.

(Comparative Example 3: Composition K)
As Comparative Example 3, 10 parts by mass of silica (trade name: nip seal AQ, water content of 5.5% by weight calculated by weight reduction method, manufactured by Tosoh Silica Co., Ltd.) was added to 100 parts by mass of 150 L butadiene, and Banbury. The mixture was kneaded at 110 ° C. for 3 minutes with a mixer.

For the compositions A to L and 150 L butadiene prepared as described above, the ratio of stationary phase hydrogen nuclei (T2S (y)) was measured and calculated by the following method. The calculation results are shown in Tables 1 and 2.
<Measurement and calculation of T2S>
Each polymer cut into approximately 1 mm square was set in a sample tube, and MSE was measured under a condition of 40 ° C. using a Bruspec minispec mq20polymer research system. The ratio y of stationary phase hydrogen nuclei was calculated from the obtained FID signal.

<Evaluation method of vulcanized rubber composition>
For the compositions A to J and 150 L butadiene, rubber compositions having the compounding formulations shown in Tables 3 and 4 were prepared, and the following vulcanized rubber compositions obtained by vulcanization under the conditions of 145 ° C. and 33 minutes, According to the method, (1) loss tangent (tan δ) and (2) wear resistance were measured. The measurement results are shown in Tables 1 and 2.

(1) Loss tangent (tan δ)
A test piece was prepared from each vulcanized rubber composition, and tan δ was measured under the conditions of an initial load of 160 g, a dynamic strain of 2%, a frequency of 52 Hz, and a temperature of 25 ° C. using a viscoelastic spectrometer manufactured by Toyo Seiki Co., Ltd. Measured and indicated by an index with Comparative Example 1 as 100. It shows that low exothermal | heat_emitting property is so favorable that the numerical value of tan-delta is small.

(2) Abrasion resistance (index)
A wear amount was measured at a room temperature with a slip rate of 60% using a Lambourn type wear tester, and displayed as an index with the reciprocal of Comparative Example 3 taken as 100. The higher the value, the better the wear resistance.

* 1: Polymers A to J or 150 L butadiene * 2: Tosoh Silica Corporation: Nip seal AQ
* 3: Product name “A / O Mix” (Process Oil), manufactured by Sankyo Oil Chemical Co., Ltd.
* 4: Product name “Si75” manufactured by Degussa
* 5: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., knock rack 6C
* 6: Ouchi Shinsei Chemical Co., Ltd .: Noxeller MZ
* 7: Ouchi Shinsei Chemical Co., Ltd .: Noxeller NS

  FIG. 4 shows a correlation diagram (graph) of the amount of silica in the polymer composition in Examples and Comparative Examples, and the ratio (y) of hydrogen nuclei in the stationary phase in the hydrogen nuclei. The straight line displayed in the graph of FIG. 4 is a straight line of y = 0.02x + 0.2. From the results of Tables 1 and 2 and FIG. 4, a vulcanized rubber composition excellent in low heat build-up is obtained by using the polymer composition of the present invention, that is, the polymer composition satisfying y ≧ 0.02x + 0.2. It was confirmed that it could be manufactured.

  The production method of the polymer composition of the present invention and the polymer composition produced by the production method are suitable for production of rubber products that require addition of silica, for example, tire members (particularly, tire tread members). Is available.

Claims (6)

A method for producing an unvulcanized polymer composition comprising 2 parts by mass or more of silica with respect to 100 parts by mass of a polymer component,
A polymer composition is produced by adding silica having a water content of 0.1 to 20% by weight to the polymerization catalyst composition used for the polymerization reaction of the monomer constituting the polymer component,
The polymer component is either a polymer of only a conjugated diene compound, or a polymer of a conjugated diene compound and a non-conjugated olefin,
The polymerization catalyst composition has the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different, and Y is from group 1 of the periodic table When it is a selected metal, a is 1 and b and c are 0. When Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from group 13 of the periodic table, a, b and c are 1). And a third element containing 2 parts by mass or more of silica with respect to 100 parts by mass of the polymer component, and then a rare earth element compound or the rare earth element Adding a first element which is a rare earth element-containing compound including a reaction product of a compound and a Lewis base,
The proportion y of stationary phase hydrogen nuclei in the hydrogen nuclei in the polymer composition is
y ≧ 0.02x + 0.2
A method for producing a polymer composition, characterized by satisfying the formula: (x is the compounding amount (part by mass) of silica, and y is the ratio of stationary phase hydrogen nuclei in hydrogen nuclei).   The method for producing a polymer composition according to claim 1, wherein the polymer component is unmodified.   The manufacturing method of the polymer composition of Claim 1 whose compounding quantity of a silane coupling agent is less than 5 mass parts with respect to 100 mass parts of said polymer components.   A method for producing a rubber composition, wherein the polymer composition produced by the method according to any one of claims 1 to 3 is used as a rubber component.   A method for producing a crosslinked rubber composition, wherein the rubber composition produced by the method according to claim 4 is crosslinked.   A method for producing a tire, comprising using the crosslinked rubber composition produced by the method according to claim 5.

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