JP6591244B2 - Rubber composition for tire - Google Patents

Description

  The present invention relates to a modified olefin polymer, specifically, a modified olefin polymer obtained by silane-modifying an α-olefin polymer polymerized with a metallocene catalyst having a specific amount of terminal unsaturated groups, The present invention mainly relates to a modified olefin polymer that can be suitably used in a tire rubber composition.

In recent years, there has been an increasing demand for lower fuel consumption of automobiles, and tire rubber materials that reduce the rolling resistance of tires have been demanded, and various devices have been made.
For example, when trying to reduce the rolling resistance of tires, the amount of carbon black filling has been reduced or the use of carbon black with a large particle size has been used, but the reinforcement, wear resistance, wet grip performance, etc. have decreased. In order to solve these problems, it is known to use silica. However, silica easily aggregates, resulting in problems such as insufficient dispersion of silica particles in the rubber and an increase in the Mooney viscosity of the rubber composition. Therefore, various methods for improving the dispersibility of silica such as the use of a silane coupling agent have been proposed.
Silane coupling agents are thought to reduce rolling resistance by binding to silanol groups on the silica surface to prevent silica from agglomerating and by combining non-agglomerated silica and diene rubber via the silane coupling agent. Yes.

  Patent Document 1 describes a rubber-silica composite obtained by intramolecular condensation of a silane-modified diene rubber polymer and a silane monomer. Patent Document 2 describes a modified conjugated diolefin polymer obtained by reacting an active living anion terminal of a conjugated diolefin polymer with an alkoxysilane sulfide compound having a specific structure (sulfide-based silane coupling agent), This material forms a Si—O—Si bond with silica and co-vulcanizes with other rubber used in the rubber composition at the time of vulcanization due to the S—S bond of the sulfide-based silane coupling agent part. .

  Patent Document 3 describes a rubber composition for tires that contains anhydrous silica and hydrous silica in a rubber component and further contains a silane coupling agent. Since normally used hydrous silica has many silanol groups on the surface, it is difficult to cover all the silanol groups even by using a silane coupling agent. When there are problems that cannot be avoided, anhydrous silica is also blended to solve these problems. Patent Document 4 describes a pneumatic tire including a sidewall composed of a rubber composition containing a rubber component, silica and a specific silane coupling agent, and containing a specific conjugated diene polymer. Has been.

In any of the inventions described in these patent documents, silica is dispersed by bonding diene rubber and silica through modification of diene rubber or use of a silane coupling agent (usually sulfide silane coupling agent). An object of the present invention is to obtain a tire rubber composition having reduced rolling resistance.
In other words, silica is directly bonded to the diene rubber by the silane coupling agent, but since the silane coupling agent itself is a low molecular weight compound, it becomes a segment with low mobility in the rubber composition, and the rolling resistance is reduced. Although it contributes to the brake performance, the brake performance is reduced.

Japanese Patent Laying-Open No. 2015-30757 JP-A-11-166020 JP 2003-192842 A JP2015-120805A

  The present invention has been made in view of the above circumstances, and when used in a tire rubber composition used for a tread, compared to a sulfide-based silane coupling agent conventionally used for a tire rubber composition. An object of the present invention is to provide a modified olefin polymer having a silica dispersion function so that a tire rubber composition having an improved balance of low rolling resistance and braking performance can be obtained.

As a result of extensive research, the inventor has achieved the above object by using a modified olefin polymer obtained by silane-modifying an α-olefin polymer polymerized with a metallocene catalyst having a specific amount of terminal unsaturated groups. It was found that this was achieved, and the present invention was completed.
That is, the present invention provides the following modified olefin polymer and method for producing the same.

(1) A modified olefin polymer satisfying the following (a) to (g).
(A) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g.
(B) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0-100 ° C.
(C) The half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed.
(D) The weight average molecular weight (Mw) is 1,000 to 500,000.
(E) The alkoxysilyl group concentration is 0.01 to 50% by mass.
(F) The number of terminal unsaturated groups per molecule is 0.4 or more.
(G) 50 mol% or more of the olefin monomers constituting the polymer are one or more monomers selected from α-olefins having 3 to 28 carbon atoms.
(2) The modified olefin polymer according to the above (1), wherein Tan δ at 0 ° C. of dynamic viscoelasticity when solid is larger than 0.1 and Tan δ at 60 ° C. is smaller than 0.1.
(3) The modified olefin polymer according to the above (1) or (2), wherein the weight average molecular weight (Mw) is 1,000 to 60,000.
(4) A tire rubber composition comprising the modified olefin polymer according to any one of (1) to (3), a diene rubber polymer, silica and sulfur.
(5) The α-olefin polymer produced using a metallocene catalyst is modified with a radical initiator and a monomer having a silane group and an ethylenically unsaturated group, (1) The manufacturing method of the modified olefin polymer in any one of-(3).
(6) The metallocene catalyst reacts with (i) a transition metal compound represented by the following general formula (I), and (ii) (ii-1) the transition metal compound of component (i) or a derivative thereof. The method for producing a modified olefin polymer according to (5) above, comprising a compound capable of forming an ionic complex and (ii-2) a component selected from aluminoxane.

[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure via A ¹ and A ² In addition, they may be the same or different from each other, X represents a σ-bonded ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group _{, -O -, - CO -,} - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]

  The modified olefin polymer of the present invention is obtained by silane-modifying an α-olefin polymer polymerized with a metallocene catalyst having a specific amount of terminal unsaturated groups, and the alkoxysilyl group of the modified olefin polymer is The dispersibility of the silica in the tire rubber composition is improved by binding to the silica surface and the terminal unsaturated group reacting with the sulfur component during the vulcanization reaction of the rubber component. That is, the modified olefin polymer of the present invention can be said to be a macrosilane coupling molecule (agent) obtained by modifying an α-olefin polymer, and this can highly disperse silica. As a result, it is expected to reduce the rolling resistance of the tire and improve the balance of the brake performance while suppressing the heat loss due to the friction between the silicas.

FIG. 1 is an SEM photograph of a cross section of a sample from (a) the resin composition of Example 4, (b) the resin composition of Comparative Example 2, and (c) the resin composition of Comparative Example 3.

(Modified olefin polymer)
The modified olefin polymer of the present invention has an alkoxysilyl group and a terminal unsaturated group, and satisfies the following (a) to (g).
(A) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g.
(B) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0-100 ° C.
(C) The half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed.
(D) The weight average molecular weight (Mw) is 1,000 to 500,000.
(E) The alkoxysilyl group concentration is 0.01 to 50% by mass.
(F) The number of terminal unsaturated groups per molecule is 0.4 or more.
(G) 50 mol% or more of the olefin monomers constituting the polymer are one or more monomers selected from α-olefins having 3 to 28 carbon atoms.

In addition to the above (a) to (g), the modified olefin polymer used in the present invention is further reduced in crystallinity by satisfying at least one of the following (h) to (k). Tan δ in the vicinity of ° C. is not small, and grip performance is not lowered.
(H) Mesopentad fraction [mmmm] is 20 mol% or more and less than 80 mol%, or mesodyad fraction [m] is 45 mol% or more and less than 90 mol%.
(I) Racemic meso racemic meso pentad fraction [rmrm] exceeds 2.5 mol%.
(J) [mm] × [rr] / [mr] ² is 2.0 or less.
(K) [rrrr] / (1- [mmmm]) is 0.1 or less.

(Intrinsic viscosity [η])
The modified olefin polymer of the present invention has an intrinsic viscosity [η] measured at 135 ° C. in tetralin of 0.01 to 2.5 dl / g, preferably 0.1 to 2.0 dl / g. Preferably it is 0.1-1.5 dl / g, More preferably, it is 0.1-1.0 dl / g, More preferably, it is 0.1-0.8 dl / g. When the intrinsic viscosity of the modified olefin polymer is increased, the mixing property with the rubber is deteriorated. As a result, the dispersibility of the silica in the rubber is deteriorated, so that the balance between the low rolling resistance and the braking performance of the rubber composition is deteriorated. .

The intrinsic viscosity [η] is calculated by measuring the reduced viscosity (ηSP / c) in tetralin at 135 ° C. with an Ubbelohde viscometer, and using the following equation (Haggins equation).
ηSP / c = [η] + K [η] ² c
ηSP / c (dl / g): Reduced viscosity [η] (dl / g): Intrinsic viscosity c (g / dl): Polymer viscosity K = 0.35 (Haggins constant)

(Melting point (Tm-D))
The melting point (Tm-D) of the modified olefin polymer is not observed or is 0 to 100 ° C. from the viewpoint of improving the dispersibility of the modified olefin polymer in the rubber composition. When the melting point is observed, from the same viewpoint, it is preferably 50 to 100 ° C, more preferably 55 to 90 ° C, and further preferably 57 to 80 ° C.
In the present invention, a differential scanning calorimeter (manufactured by Perkin Elmer, trade name: “DSC-7”) was used, and 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then 10 ° C./min. The peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at is defined as the melting point (Tm-D).
The melting point (Tm-D) can be controlled by appropriately adjusting the monomer concentration and reaction pressure.

(Semi-crystallization time)
The semi-crystallization time of the modified olefin polymer measured by a differential scanning calorimeter (DSC) is 3 minutes or more from the viewpoint of slow crystallization rate, or is measured by a differential scanning calorimeter (DSC). No crystallization peak is observed. Preferably it is 10 minutes or more, More preferably, it is 30 minutes or more. When the crystallization rate is so slow that the half crystallization time exceeds 60 minutes, a clear crystallization peak may not be observed.
By satisfying the above-mentioned half-crystallization time, the wax component is first solidified when the tire is cooled and solidified, so that the bleed-out of the wax component due to crystallization of the modified olefin polymer can be prevented.
The “half crystallization time” in the present invention indicates that measured by the following measurement method.

<Measuring method of semi-crystallization time>
Using a differential scanning calorimeter (DSC) (manufactured by Perkin Elmer, trade name: “DSC-7”), the measurement is performed by the following method.
(1) Hold 10 mg of sample at 25 ° C. for 5 minutes, raise the temperature to 320 ° C. at 320 ° C./second and hold for 5 minutes. By cooling to 25 ° C. at 320 ° C./second and holding for 300 minutes, the time change of the heat generation amount during the isothermal crystallization process is measured.
(2) When the integrated value of the calorific value from the start of isothermal crystallization to the completion of crystallization is 100%, the time from the start of isothermal crystallization until the integrated value of the calorific value becomes 50% is semi-crystallized. Define as time.

(Mesopentad fraction [mmmm])
The mesopentad fraction [mmmm] is an index representing the stereoregularity of the olefin polymer, and the stereoregularity increases as the mesopentad fraction [mmmm] increases.
In the present invention, when the olefin polymer before modification is a homopolymer, the mesopentad fraction [mmmm] of the modified olefin polymer is preferably 20 to 80 mol%, more preferably 30 to 80 mol%, More preferably, it is 40-75 mol%. When the mesopentad fraction [mmmm] is within this range, the crystallinity is low, the crystallization rate is relatively slow, and the time until solidification during molding becomes long. Due to the low crystallinity, separation from silica and wax components due to crystallization of the modified olefin polymer can be suppressed.

(Mesodyad fraction [m])
The meso-dyad fraction [m] is an index representing the stereoregularity of the olefin polymer, and the stereoregularity increases as the meso-dyad fraction [m] increases.
In the present invention, when the olefin polymer before modification is a copolymer containing an ethylene monomer, the mesodyad fraction [m] of the modified olefin polymer is preferably 45 mol% or more and less than 90 mol%, more Preferably it is 50-85 mol%, More preferably, it is 60-80 mol%. When the meso-dyad fraction [m] is within this range, the crystallinity is low, the crystallization rate is relatively slow, and the time until solidification during molding becomes long.

The mesopentad fraction [mmmm] and the mesodyad fraction [m] of the modified olefin polymer are ¹³ in accordance with the method proposed in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. Measured using C-NMR. Further, the racemic pentad fraction [rrrr], the racemic meso racemic meso pentad fraction [rmrm], the meso triad fraction [mm], the racemic triad fraction [rr] and the meso racemic triad fraction [mr] described above are also described above. Measured by the method.
When the olefin polymer before modification is a polyolefin mainly composed of polypropylene (90% by mass or more of propylene), the mesopentad fraction [mmmm] can be measured by the following method.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

The method for calculating the mesopentad fraction M is as follows.
M = (m / S) × 100
R = (γ / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

When the olefin polymer before modification is a polyolefin containing polybutene as a main component (butene of 90% by mass or more), the mesodyad fraction [m], the mesopentad fraction [mmmm], the racemic pentad fraction are obtained by the following methods. The rate [rrrr], the racemic meso racemic meso pentad fraction [rmrm], the meso triad fraction [mm], the racemic triad fraction [rr] and the meso racemic triad fraction [mr] were reported by Asakura et al. Journal, 16, 717 (1984) ", J. Am. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It can be measured according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the mesopentad fraction in the poly (1-butene) molecule can be determined by measuring the signals of methylene group and methine group using ¹³ C nuclear magnetic resonance spectrum.
^{The 13} C nuclear magnetic resonance spectrum can be measured using the above apparatus and conditions.

When the olefin polymer is a polyolefin mainly composed of an α-olefin having 6 to 28 carbon atoms, the mesodyad fraction [m], the mesopentad fraction [mmmm], and the racemic pentad fraction [rrrr] are obtained by the following methods. The racemic meso racemic meso pentad fraction [rmrm], the meso triad fraction [mm], the racemic triad fraction [rr] and the meso racemic triad fraction [mr] were determined by Asakura et al., “Macromolecules, 24, 2334 (1991). The meso fraction, the racemic fraction and the racemic meso-racemic meso fraction in the pentad unit in the polyolefin molecule measured by the methyl group signal of the ¹³ C-NMR spectrum in accordance with the method proposed in the above. As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
^{The 13} C nuclear magnetic resonance spectrum can be measured using the above apparatus and conditions.

(Racemic meso racemic meso pentad fraction [rmrm])
The racemic meso racemic meso pentad fraction [rmrm] is an index representing the randomness of the stereoregularity of the olefin polymer, and the greater the value, the greater the randomness of the olefin polymer.
The racemic meso racemic meso pentad fraction [rmrm] of the modified olefin polymer used in the present invention is preferably more than 2.5 mol%, more preferably 2.6 mol% or more, still more preferably 2.7 mol%. That's it. The upper limit is usually preferably about 10 mol%, more preferably 7 mol%, still more preferably 5 mol%, and particularly preferably 4 mol%. When the value is within the range, the randomness increases, the crystallinity of the modified olefin polymer is lowered, and the dispersibility in the rubber composition can be improved.

([Mm] × [rr] / [mr] ² )
The value of [mm] × [rr] / [mr] ² indicates an index of randomness of the olefin polymer, and the closer to 1, the higher the randomness.
In the modified olefin polymer used in the present invention, [mm] × [rr] / [mr] ² is preferably 2.0 or less, more preferably 0.5 to 1.8, still more preferably 0.5 to 1. .5. When the value is within this range, the crystallinity of the modified olefin polymer is lowered and the dispersibility in the rubber composition is improved. In addition, the unit of [mm], [rr], and [mr] in the above is mol%.

([Rrrr] / (1- [mmmm]))
The value of [rrrr] / (1- [mmmm]) is obtained from the mesopentad fraction [mmmm] and the racemic pentad fraction [rrrr] and is an index indicating the uniformity of the regular distribution of the olefin polymer. . When the olefin polymer before modification is a homopolymer, the value of [rrrr] / (1- [mmmm]) of the modified olefin polymer is preferably 0.1 or less, more preferably 0. 0.001 to 0.05, more preferably 0.001 to 0.04, and particularly preferably 0.01 to 0.04. When the value is within this range, the high crystallinity is reduced and the dispersibility in the rubber composition is improved.

(Weight average molecular weight (Mw))
The weight average molecular weight (Mw) of the modified olefin polymer of the present invention is 1,000 to 500,000, more preferably 1,000 to 400, from the viewpoint of low temperature characteristics and improved dispersibility in the rubber composition. 1,000, more preferably 1,000 to 300,000, more preferably 1,000 to 200,000, still more preferably 1,000 to 200,000, and still more preferably 1,000 to 60,000.

(Molecular weight distribution (Mw / Mn))
From the viewpoint of improving dispersibility in the rubber composition, the modified olefin polymer of the present invention preferably has a molecular weight distribution (Mw / Mn) of 4.0 or less, more preferably 3.5 or less, and even more preferably 3 .2 or less, more preferably 3.0 or less. The molecular weight distribution is preferably 1.0 or more, more preferably 1.2 or more.

  In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those in terms of polystyrene measured by the following apparatus and conditions, and the molecular weight distribution (Mw / Mn) is the weight average molecular weight (Mw). ) And the number average molecular weight (Mn).

<GPC measurement device>
Column: “TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram “WATERS 150C” manufactured by Waters Corporation
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(Alkoxysilyl group concentration)
The modified olefin polymer of the present invention has an alkoxysilyl group.
The alkoxysilyl group is not particularly limited, but is preferably a trialkoxysilyl group having an alkoxy group having 1 to 20 carbon atoms, more preferably a trialkoxysilyl group having an alkoxy group having 1 to 10 carbon atoms. The alkoxy group may be linear or branched.
Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, and a tripropyloxysilyl group, and a trimethoxysilyl group or a triethoxysilyl group is preferable.

  The modified olefin polymer of the present invention has an alkoxysilyl group concentration in terms of triethoxysilyl group of 0.01 to 50% by mass, preferably 0.01 to 30% by mass, more preferably 0.1 to 30% by mass. 20 mass%, More preferably, it is 0.5-10 mass%, More preferably, it is 0.5-5 mass%, More preferably, it is 1.0-4 mass%.

  In the modified olefin polymer of the present invention, when the alkoxysilyl group concentration in terms of triethoxysilyl group is 0.01% by mass or more, the crosslinking performance can be improved, and a cured product can be easily obtained. When the content is less than or equal to mass%, a cured product having an appropriate hardness is obtained, and curing proceeds in a state where a hydroxyl group-containing additive such as silica is appropriately dispersed. That is, a modified olefin polymer having an alkoxysilyl group concentration within the above range, when a curable composition is obtained using this, the crosslinking rate is reasonably fast because the alkoxysilyl group concentration is high, and the curing The strength of the later cured product is high, and the hydroxyl group-containing additive is highly dispersed to improve the physical property balance.

The above-mentioned alkoxysilyl group concentration in terms of triethoxysilyl group can be determined according to the following.
First, the silyl element concentration is measured by the following method.
Concentration of silyl element is as follows: 0.1 g of sample is heated overnight (550 ° C.) in an electric furnace, a sample solution is prepared by alkali melting of ash, and ICP emission spectroscopic analysis (Agilent Technology, 720-ES) Then, the concentration of Si element is measured.
The value of the measured silyl element concentration is defined as a mass%. Use the numerical value to convert according to the following formula.
Triethoxysilyl group equivalent alkoxysilyl group concentration = a × 163.3 / 28.1 (mass%)
The presence of an alkoxysilyl group in the modified olefin polymer means that hydrogen on the carbon atom next to the oxygen atom of the alkoxysilyl group appearing in the vicinity of 3.7 to 4.1 ppm using ¹ H-NMR. It can be confirmed by the presence or absence of a peak derived from an atom (a silyl group having an alkoxy group having 2 or more carbon atoms) or a singlet peak (in the case of a trimethoxysilyl group) appearing around 3.6 ppm.

(Terminal unsaturated group concentration)
The number of terminal unsaturated groups in the present invention means the total number of vinyl groups and vinylidene groups. When only a vinyl group is present, it means the concentration and number of only the vinyl group, and when both vinyl group and vinylidene group are included, it means the concentration and number of both sums.
Examples of the terminal unsaturated group include a vinyl group, a vinylidene group, and a trans (vinylene) group. The terminal unsaturated group defined in this specification means a vinyl group and a vinylidene group. Vinyl groups and vinylidene groups are radically polymerizable and have a wide range of applications for various reactions and can meet various requirements.
In the modified olefin polymer of the present invention, the number of terminal unsaturated groups per molecule is 0.4 or more. If it is less than 0.4, the crosslinking reaction does not proceed sufficiently during the vulcanization reaction in the presence of natural rubber or styrene / butadiene rubber, such being undesirable. In this respect, 0.5 or more is preferable, and 0.6 or more is more preferable. Moreover, 2.0 or less is preferable and 1.5 or less is more preferable from a viewpoint of improving the dispersibility in the rubber | gum of the modified olefin polymer which leads to the dispersibility of a silica.

The terminal unsaturated group concentration is measured and calculated as follows.
Terminal vinylidene groups appearing in δ 4.8 to 4.6 (2H), terminal vinyl groups appearing in δ 5.9 to 5.7 (1H) and δ 1.05 to 0.60 (1H-NMR measurement obtained from ¹ H-NMR measurement) Based on the methyl group appearing in 3H), the terminal unsaturated group concentration (C) (mol%) was calculated.
CH _{2 of} vinylidene group (4.8 to 4.6 ppm) (i)
Vinyl group CH (5.9 to 5.7 ppm) (ii)
Side chain terminal CH ₃ (1.05 to 0.60 ppm) (iii)
Vinylidene group amount = [(i) / 2] / [(iii) / 3] × 100 mol%
Vinyl group content = (ii) / [(iii) / 3] × 100 mol%
Terminal unsaturated group concentration (C) = [vinylidene group amount] + [vinyl group amount]

From the terminal unsaturated group concentration (C, mol%) calculated by the above method, the number average molecular weight (Mn) and the olefin monomer molecular weight (M) determined from the gel permeation chromatograph (GPC), one molecule The number of terminal unsaturated groups per unit was calculated.
Number of terminal unsaturated groups per molecule (number) = (Mn / M) × (C / 100)

(Dynamic viscoelasticity when solid)
The modified olefin polymer of the present invention has a dynamic viscoelasticity when solid, Tan δ at 0 ° C. is larger than 0.1 and Tan δ at 60 ° C. is smaller than 0.1.
When the dynamic viscoelasticity when solid satisfies the above, when a modified olefin polymer is added to the tire rubber composition described later, the energy absorption near 10,000 Hz that affects the braking performance is large, and the rolling resistance is reduced. It can be expected that a tire rubber composition excellent in the balance of energy saving (low fuel consumption) and braking performance of the tire will be obtained because the energy absorption in the vicinity of 100 Hz that contributes becomes low. From the above viewpoint, Tan δ at 0 ° C. is preferably larger than 0.14, more preferably larger than 0.16. Further, Tan δ at 60 ° C. is preferably smaller than 0.08, more preferably smaller than 0.05.

  In addition, the range of the said dynamic viscoelasticity is a range normally calculated | required by the dynamic viscoelasticity of the rubber composition for tires. That is, it is preferable that the component (modified olefin polymer) used in the tire rubber composition has the above dynamic viscoelasticity range.

Dynamic viscoelasticity can be measured under the following conditions in a nitrogen atmosphere using a viscoelasticity measuring device (trade name: DMS 6100 (EXSTAR6000) manufactured by SII Nano Technology).
<Measurement conditions>
Measurement mode: Tensile mode Measurement temperature: Among −150 ° C. to 230 ° C., three points of −50 ° C., 25 ° C. and 150 ° C. were observed.
Temperature increase rate: 5 ° C / min
Measurement frequency: 1Hz
Sample size: length 10mm, width 4mm, thickness 1mm (press molded product)

  When the modified olefin polymer is liquid at normal temperature (25 ° C.), 2 parts by mass of a curing accelerating catalyst described later is added to 100 parts by mass of the modified olefin polymer, and the normal temperature (25 ° C.) and humidity 50%. Then, the dynamic viscoelasticity of the solid obtained by curing for 24 hours is measured.

  The modified olefin polymer of the present invention is a low crystalline olefin polymer, and has a higher Tg than rubber, so that the rolling resistance is reduced. Further, Tan δ near 0 ° C. is high and Tan δ near 60 ° C. is low, which is considered to contribute to improving the balance between tire fuel efficiency and braking performance. Furthermore, since the affinity with the wax component is high, it is considered that the bleed-out can be suppressed and cracking of the tire due to exhaustion of the wax component can be suppressed.

(Olefin monomer)
The olefin monomer constituting the olefin polymer which is a raw material of the modified olefin polymer of the present invention is one or more monomers selected from ethylene and an α-olefin having 3 to 28 carbon atoms, and an α having 3 to 28 carbon atoms. -50 mol% or more of olefins. Examples of the α-olefin having 3 to 28 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene and 1- Examples include dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-icocene. The α-olefin monomer is preferably an α-olefin having 3 to 24 carbon atoms, more preferably an α-olefin having 3 to 12 carbon atoms, particularly preferably an α-olefin having 3 or 4 carbon atoms (ie, propylene monomer, 1- Butene monomer), an α-olefin having 6 to 12 carbon atoms.
50 mol% or more of the olefin structural unit in the modified olefin polymer of the present invention is preferably at least one monomer selected from α-olefins having 3 or 4 carbon atoms (that is, propylene monomer, 1-butene monomer), More preferably, it is 65 mol% or more, More preferably, it is 75 mol% or more, More preferably, it is 80 mol% or more.
In addition, the modified olefin polymer of this invention may also contain monomers other than an olefin in the range which does not inhibit the effect of this invention.

(Method for producing modified olefin polymer)
The modified olefin polymer used in the present invention can be produced by modifying the olefin polymer with silane.
The olefin polymer is obtained by polymerizing one or more monomers selected from ethylene and an α-olefin having 3 to 28 carbon atoms, and the α-olefin having 3 to 28 carbon atoms is 50 mol% or more, As described above, preferable α-olefins are α-olefins having 3 or 4 carbon atoms and α-olefins having 6 to 12 carbon atoms.

The olefin polymer can be produced, for example, by using a metallocene catalyst comprising a combination of the following components (i) and (ii) and using hydrogen as a molecular weight regulator.
Further, the following component (iii) may be added to the metallocene catalyst.
(I) Transition metal compound containing a metal element belonging to Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group. (Ii) (ii-1) (I) a compound capable of forming an ionic complex by reacting with the component transition metal compound or a derivative thereof; and (ii-2) a component selected from aluminoxane. (Iii) an organoaluminum compound. Specifically, WO2008 / 047860 Can be produced by the method disclosed in the above.

Examples of the transition metal compound containing a metal element belonging to Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group as the component (i) include, for example, the following general formula: The bibridged complex represented by (I) is mentioned.

In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table. Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. Metal etc. are mentioned. Among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like, and zirconium is most preferable from the viewpoint of the yield of olefin polymer and catalytic activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group (>CR-,> C <) and silicon-containing group (>SiR-,> Si <) (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E ¹ and E ² is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
The substituent of the substituted cyclopentadienyl group, substituted indenyl group, or substituted heterocyclopentadienyl group has 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). A substituent such as a hydrocarbon group, a silicon-containing group or a heteroatom-containing group is shown.
X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 40 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, cyclohexyl groups, octyl groups and other alkyl groups; vinyl groups, propenyl groups, cyclohexenyl groups, and the like. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthryl group, and the like. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 40 carbon atoms include dialkyl phosphide groups, diethyl phosphide groups, dipropyl phosphide groups, dibutyl phosphide groups, dihexyl phosphide groups, dicyclohexyl phosphide groups, and dioctyl phosphide groups. Fido group; dialkenyl phosphide group such as divinyl phosphide group, dipropenyl phosphide group, dicyclohexenyl phosphide group; bis such as dibenzyl phosphide group, bisphenylethyl phosphide group, bisphenylpropyl phosphide group Arylalkyl phosphide group; diphenyl phosphide group, ditolyl phosphide group, bisdimethylphenyl phosphide group, bistrimethylphenyl phosphide group, bisethylphenyl phosphide group, bispropylphenyl phosphide group, bisbiphenyl phosphide group I de group, bisnaphthyl phosphide group, bis methyl naphthyl phosphide group, bis anthracenyl phosphide group, and a diarylamino phosphide group such as bis phenanthryl phosphide group.

Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, Tiger Se Nils sulfide group, an aryl sulfide groups such phenanthryl sulfide group.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, stearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like. Examples of the amine include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine. Alkylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine, etc .; arylalkylamines such as phenylethylamine, phenylpropylamine; phenylamine, diphenylamine, dinaphthylamine, etc. Arylamine is mentioned.

  Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; anisole Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, dioxane, etc. Can be mentioned.

  Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specific examples include monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Monoalkenes such as phosphine, propenylphosphine, cyclohexenylphosphine, etc. Dialkenylphosphine in which two alkenyls are substituted for phosphine and phosphine hydrogen atoms; Trialkenylphosphine in which three alkenyls are substituted for phosphine hydrogen; Arylalkylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine in which three hydrogen atoms are substituted by aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, anthracenylphosphine, phenanthrylphosphine; phosphine water Atom alkyl aryl two substituted di (alkylaryl) phosphine; arylphosphine such as a hydrogen atom of phosphine alkylaryl three substituted with tri (alkylaryl) phosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms or a silicon-containing group. Examples of such a bridging group include those represented by the following general formula (a), and specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, and a cyclohexylidene group. , 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldi A silylene group etc. can be mentioned. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

(D is a group 14 element of the periodic table, and examples thereof include carbon, silicon, germanium and tin. R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other, and may be bonded to each other to form a ring structure.

  Specific examples of the transition metal compound represented by the general formula (I) include specific examples described in WO2008 / 066168. Moreover, the analogous compound of the metal element of another group may be sufficient. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

Among the transition metal compounds represented by the general formula (I), compounds represented by the following general formula (II) are preferable.

In the above general formula (II), M represents a metal element belonging to Groups 3 to 10 of the periodic table, and A ^1a and A ^2a each represent a crosslinking group represented by the general formula (a) in the above general formula (I). CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C (CH ₃ ) ₂ C, (CH ₃ ) ₂ Si and (C ₆ H ₅ ) ₂ Si are preferred. A ^1a and A ^2a may be the same as or different from each other. R ^{4 to} R ¹³ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the silicon-containing group are the same as those described in the general formula (I). Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis ( (Trifluoro) phenyl group, fluorobutyl group and the like. Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups. Specifically, nitrogen-containing groups such as a dimethylamino group, a diethylamino group, and a diphenylamino group; a phenylsulfide group, a methylsulfide group, and the like Sulfur-containing groups of: phosphorus-containing groups such as dimethylphosphino groups and diphenylphosphino groups; oxygen-containing groups such as methoxy groups, ethoxy groups, and phenoxy groups. Among these, as R ⁴ and R ⁵ , a group containing a hetero atom such as a halogen atom, oxygen, or silicon, or a hydrocarbon group having 1 to 20 carbon atoms is preferable because of high polymerization activity. R ^{6 to} R ¹³ are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as in general formula (I). q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

  Of the transition metal compounds represented by the above general formula (II), when both indenyl groups are the same, examples of the transition metal compounds belonging to Group 4 of the periodic table include specific examples described in WO2008 / 066168. . Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

On the other hand, among the transition metal compounds represented by the above general formula (II), when R ⁵ is a hydrogen atom and R ⁴ is not a hydrogen atom, the transition metal compound of Group 4 of the periodic table is disclosed in WO2008 / 066168. Specific examples of the description are given. Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

(Ii) (ii-1) The compound that can react with the transition metal compound of the component (i) to form an ionic complex is a relatively low molecular weight, high-purity end group. A borate compound is preferable from the viewpoint of obtaining a saturated olefin polymer and high catalytic activity. Specific examples of the borate compound include those described in WO2008 / 066168. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen and transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.
Examples of the above-mentioned (ii) (ii-2) aluminoxane include known chain aluminoxanes and cyclic aluminoxanes.

The catalyst used in the method for producing an olefin polymer may be a combination of the component (i) and the component (ii), and an organoaluminum compound is used as the component (iii) in addition to the component (i) and the component (ii). May be.
(Iii) Component organoaluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride. Dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.
Of these, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum are more preferable. preferable.

The amount of component (i) used is usually 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁵ mol / L, preferably 0.15 × 10 ^{−6 to} 1.3 × 10 ⁻⁵ mol / L, more preferably ^{0.2 × 10 -6 ~1.2 × 10 -5} mol / L, particularly preferably ^{0.3 × 10 -6 ~1.0 × 10 -5} mol / L. (I) When the usage-amount of a component is 0.1 * 10 < ^-6 > mol / L or more, catalyst activity is fully expressed, and when it is 1.5 * 10 < ^-5 > mol / L or less, ^{superposition} | polymerization heat is easy. Can be removed.
(Ii) When the component (ii-1) is used, the use ratio (i) / (ii-1) of the component (i) and the component (ii-1) is preferably 10/1 to 1 in molar ratio. 1/100, more preferably 2/1 to 1/10. When (i) / (ii-1) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed. Further, there is no fear that a large amount of boron exists in the target olefin polymer.
(Ii) When the component (ii-2) is used, the usage ratio (i) / (ii-2) of the component (i) and the component (ii-2) is preferably 1/1 to A range of 1/1000000, more preferably 1/10 to 1/10000 is desirable. When deviating from this range, the catalyst cost per unit weight polymer becomes high, which is not practical.
Moreover, (ii-1) and (ii-2) can also be used individually or in combination of 2 or more types as a catalyst component (ii).
When the component (iii) is used, the use ratio (i) / (iii) of the component (i) and the component (iii) is preferably 1/1 to 1/10000, more preferably 1/5 to 1/5 by molar ratio. 1/2000, more preferably 1/10 to 1/1000. By using the component (iii), the polymerization activity per transition metal can be improved. When (i) / (iii) is in the range of 1/1 to 1/10000, the balance between the addition effect of component (iii) and economic efficiency is good, and aluminum is contained in the target olefin polymer. There is no fear of being present in large quantities.
In the method for producing an olefin polymer, preliminary contact may be performed using the above-described component (i) and component (ii), or component (i), component (ii), and component (iii). The preliminary contact can be performed by bringing the component (i) into contact with, for example, the component (ii). However, the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the co-catalyst (ii) component used.
As the polymerization method, any of continuous type, batch type, solution polymerization, bulk polymerization and the like can be applied. However, in the present invention, the monomer concentration is controlled to be low and terminal unsaturated groups are easily generated. A continuous type or semi-batch type using a supplied solvent is preferred.

  The modified olefin polymer of the present invention is obtained by reacting an olefin polymer, a radical initiator, and a monomer having an alkoxysilyl group and an ethylenically unsaturated group (hereinafter sometimes abbreviated as a silane-modified monomer). Can be manufactured.

  The radical initiator used in the reaction of the olefin polymer with the monomer having a silane group and an ethylenically unsaturated group is not particularly limited, and conventionally known radical initiators such as various organic peroxides, azobisiso Although it can be appropriately selected from azo compounds such as butyronitrile and azobisisovaleronitrile, an organic peroxide is preferable.

Examples of the organic peroxide include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t- Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 , Α, α′bis (t-butylperoxy) diisopropylbenzene Oxides, peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxyoct , Alkyl peresters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di Examples thereof include peroxycarbonates such as -sec-butyl peroxydicarbonate and t-butylperoxyisopropyl carbonate. Of these, dialkyl peroxides are preferred. Moreover, these may be used individually by 1 type and may be used in combination of 2 or more types.
Although there is no restriction | limiting in particular as the usage-amount of a radical initiator, Preferably it is 0.01-10 mass parts with respect to 100 mass parts of alpha-olefin type polymers to be used, More preferably, it is the range of 0.01-5 mass parts. Used in

Specific examples of the monomer having a silane group and an ethylenically unsaturated group to be reacted with the α-olefin polymer include those represented by the following general formula (i).
(RO) ₃ -Si-Y (i)
(In the formula, Y is an ethylenically unsaturated group, R is an alkyl group, and three Rs may be the same or different from each other.)
The ethylenically unsaturated group has reactivity with a free radical site generated in the α-olefin polymer. Examples of the ethylenically unsaturated group include vinyl group, allyl group, butenyl group, cyclohexenyl group, cyclopentadienyl group, (meth) acryloxyalkyl group, etc., preferably vinyl group, methacryloxyalkyl group. And at least one selected from a group and an acryloxyalkyl group.
The alkyl group may be linear or branched, preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various heptyl, various octyl, various nonyl, various decanyl groups, etc. Among these, at least one selected from a methyl group and an ethyl group is preferable.
Specific examples of the silane-modified monomer include vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, and the like.

  The usage-amount of a silane modification monomer becomes like this. Preferably it is 0.1-50 mass parts with respect to 100 mass parts of olefin polymers, More preferably, it is 0.5-10 mass parts.

As a method of reacting the above-mentioned olefin polymer with a radical initiator and a silane-modified monomer, using a roll mill, a Banbury mixer, an extruder, or the like, a method of reacting by melting and kneading at a temperature of about 100 to 300 ° C., or Hydrocarbon solvents such as butane, pentane, hexane, heptane, cyclohexane, toluene, xylene, decahydronaphthalene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and appropriate organics such as liquefied α-olefins A method of reacting by solution modification at a temperature of about −50 to 300 ° C. in a solvent can be used.
In order to keep the alkoxysilyl group concentration within a predetermined range, it is preferable to carry out the reaction at a high temperature of about 120 to 200 ° C. under solvent-free conditions from the viewpoint of increasing the concentration of radicals and silane-modified monomers.

  As described above, the modified olefin polymer of the present invention can be suitably used mainly as having a silane coupling agent action in a tire rubber composition. In that case, it is preferable that the compounding quantity of a modified olefin polymer is 0.1-10 mass parts with respect to 100 mass parts of rubber components, More preferably, it is 0.5-5 mass parts.

  Examples of the diene rubber polymer used in the tire rubber composition include various rubber polymers having isoprene units and / or butadiene units in the molecule. Specific examples thereof include natural rubber (NR) and synthetic isoprene. Rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), nitrile rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber Or styrene-isoprene-butadiene copolymer rubber. These diene rubber polymers may be used alone or in combination of two or more. Among these, natural rubber, synthetic isoprene rubber, styrene butadiene rubber, or butadiene rubber is preferably used, and more preferably natural rubber or synthetic isoprene rubber is used.

Silica can be blended in the rubber composition for a tire.
The silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), etc. Among them, dry silica is preferable. Colloidal properties of the silica are not particularly limited, those which are nitrogen adsorption specific surface area (BET) 150~250m ² / g by BET method is preferably used, more preferably 180~230m ² / g. The BET of silica is measured according to the BET method described in ISO 5794.

Further, the tire rubber composition may contain a filler other than silica.
As other fillers, for example, various inorganic fillers such as carbon black, titanium oxide, aluminum silicate, clay, or talc can be used, and these can be used alone or in combination of two or more. . Among these, carbon black is preferably used.

  The carbon black is not particularly limited, and various grades of furnace carbon black such as SAF, ISAF, HAF, and FEF, which are used as rubber reinforcing agents, can be used.

  In addition to the above-described components, the tire rubber composition includes oil, zinc white, stearic acid, anti-aging agent, wax, vulcanizing agent, vulcanization accelerator, and flame retardant as long as the effects of the present invention are not impaired. Various additives generally used in rubber compositions such as a curing accelerating catalyst and a silane coupling agent can be blended.

  Examples of the vulcanizing agent include sulfur or a sulfur-containing compound (for example, sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, and alkylphenol disulfide). Or it can be used in combination of two or more. Although the compounding quantity of a vulcanizing agent is not specifically limited, It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 0.5-5 mass parts. .

  As said vulcanization accelerator, various vulcanization accelerators, such as a sulfenamide type | system | group, a thiuram type | system | group, a thiazole type | system | group, or a guanidine type | system | group, can be used, for example, any 1 type individually or in combination of 2 or more types. Can be used. Although the compounding quantity of a vulcanization accelerator is not specifically limited, It is preferable that it is 0.1-7 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 0.5-5 mass parts. is there.

The curing accelerating catalyst promotes the curing by sulfur and promotes the reaction between the macrosilane coupling agent (modified olefin polymer) and the diene rubber by sulfur. Examples of the curing accelerating catalyst include organometallic catalysts and tertiary amines.
Examples of the organic metals include organic tin metal compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate and tin octenoate, lead octenoate and lead naphthenate.
Tertiary amines include N-triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethyl Examples include aminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N′-dimethylaminoethylpiperazine, and imidazole compounds in which the secondary amine functional group of the imidazole ring is substituted with a cyanoethyl group. it can.
These may be used alone or in combination of two or more. Of the above catalysts, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctate are particularly preferable.
The content of the curing accelerating catalyst in the tire rubber composition of the present invention is preferably 0.005 to 2.0 mass%, more preferably 0.01 to 0.00% in the tire rubber composition of the present invention. 5% by mass.

For the purpose of further improving the dispersibility of silica in the rubber for tires, a conventional silane coupling agent can be added to such an extent that the effect of the present invention is not affected. Examples of the silane coupling agent include sulfide silane coupling agents, mercapto silane coupling agents, vinyl silane coupling agents, amino silane coupling agents, glycidoxy silane coupling agents, nitro silane coupling agents, Chloro-based silane coupling agents and the like can be mentioned, such as bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3- Mercaptopropyltrimethoxysilane is preferred.
Content of the said silane coupling agent in the rubber composition for tires of this invention is 15 mass% or less with respect to the total amount of silica contained in the rubber composition for tires of this invention.

  The rubber composition for tires can be prepared by kneading according to a conventional method using a commonly used Banbury mixer, kneader, roll or other mixer. That is, in the first mixing stage, the diene rubber polymer is added and mixed with the modified olefin polymer and silica together with other additives except the vulcanizing agent and the vulcanization accelerator, and then the resulting mixture is finally mixed. A rubber composition for a tire can be prepared by adding and mixing a vulcanizing agent and a vulcanization accelerator in a stage.

The modified olefin polymer of the present invention, in addition to the components added to the tire rubber composition, is a resin compatibilizer, a polyolefin emulsion, a reactive adhesive, a reactive hot melt adhesive, other adhesives, an adhesive, It can be used for applications such as a sealing material, a sealing material, a potting material, a reactive plasticizer, and a modifier.
Silicone-based adhesives and modified silicone-based adhesives are moisture-cured by reaction with moisture of isocyanate groups or alkoxysilane groups, and exhibit functions as adhesives. The modified olefin polymer of the present invention also has a structure containing a moisture curing component (alkoxysilane group) and has a molecular weight lower than that of the adhesive component, so that it can be suitably used as a viscosity modifier for the adhesive.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In addition to the above-described contents, various physical properties were measured as follows.

(Measurement of dynamic viscoelasticity)
Using a viscoelasticity measuring device (product name: DMS 6100 (EXSTAR6000) manufactured by SII Nano Technology), measurement was performed under the following conditions in a nitrogen atmosphere.
<Measurement conditions>
Measurement mode: Tensile mode Measurement temperature: Among −150 ° C. to 230 ° C., three points of −50 ° C., 25 ° C. and 150 ° C. were observed.
Temperature increase rate: 5 ° C / min
Measurement frequency: 1Hz
Sample size: length 10mm, width 4mm, thickness 1mm (press molded product)

(Measurement of melting point (Tm-D))
Using a differential scanning calorimeter (Perkin Elmer, DSC-7), 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then decreased to −10 ° C. at 5 ° C./min. The melting point (Tm-D) of the peak top of the peak observed on the highest temperature side of the melting endotherm (ΔH-D) curve obtained by raising the temperature at ° C./min was measured.

Production Example 1 [Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride]
Under a nitrogen stream, 2.5 g (7.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) and 100 ml of ether were added to a 200 ml Schlenk bottle.
After cooling to −78 ° C. and adding 9.0 ml (14.8 mmol) of a hexane solution (1.6 mol / liter) of n-butyllithium (n-BuLi), the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the resulting solid was washed with 20 ml of hexane and dried under reduced pressure to quantitatively obtain a lithium salt as a white solid.
In a Schlenk bottle, lithium salt (6.97 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) was dissolved in 50 ml of THF (tetrahydrofuran), and iodomethyl at room temperature. Trimethylsilane 2.1 ml (14.2 mmol) was slowly added dropwise and stirred for 12 hours.
The solvent was distilled off, and 50 ml of ether was added, followed by washing with a saturated ammonium chloride solution.
After liquid separation, the organic phase is dried and the solvent is removed to remove 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene). ) Was obtained (yield 84%).
Next, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. ) And 50 ml of ether. After cooling to −78 ° C., 7.4 ml (11.8 mmol) of a hexane solution (1.6 mol / liter) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 ml of hexane to obtain 3.06 g of a lithium salt as an ether adduct.
Under a nitrogen stream, 3.06 g of the lithium salt obtained above was suspended in 50 ml of toluene. This was cooled to −78 ° C., and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to −78 ° C. in advance, in toluene (20 ml) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. After the solvent of the reaction solution was distilled off, the resulting residue was recrystallized from dichloromethane to obtain (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl). 0.9 g (1.33 mmol) of yellow fine crystals of zirconium dichloride was obtained (yield 26%).
When ¹ H-NMR of the yellow microcrystals obtained above was determined, the following results were obtained.
¹ H-NMR (90 MHz, CDCl ₃ ): δ0.0 (s, —SiMe ₃ —, 18H),
_{1.02,1.12 (s, -Me 2 Si-,} 12H), 2.51 (dd, -CH 2 -, 4H), 7.1-7.6 (m, Ar-H, 8H)

Production Example 2 (Polybutene-1 polymerization)
In a heat-dried 2 liter autoclave, 600 ml of heptane, 0.6 mmol of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilyl) obtained in Production Example 1 Methylindenyl) zirconium dichloride (5.0 μmol) and dimethylanilinium tetrakispentafluorophenylborate (15.0 μmol) were added, and 0.02 MPa of hydrogen was further introduced. While raising the polymerization temperature to 70 ° C., the pressure of butene-1 was increased to 0.20 MPa at a total pressure, and continuously fed butene-1 was consumed for 60 minutes while maintaining the total pressure at 0.20 MPa. Polymerized. After completion of the polymerization reaction, 160 g of polybutene-1 was obtained by drying the reaction product under reduced pressure.
The resulting polybutene-1 has an intrinsic viscosity [η] of 0.17 deciliter / g, a weight average molecular weight (Mw) of 16,800, a molecular weight distribution (Mw / Mn) of 2.0, and stereoregularity (mesopentad fraction). : Mmmm) was 64.7 mol%, and the melting point (Tm-D) was 65.4 ° C.

Production Example 3 (Polybutene-1 polymerization)
65 g of polybutene-1 was obtained in the same manner as in Production Example 2 except that the polymerization temperature in Production Example 2 was changed to 65 ° C. instead of 70 ° C.
The resulting polybutene-1 has an intrinsic viscosity [η] of 0.41 deciliter / g, a weight average molecular weight (Mw) of 53,000, a molecular weight distribution (Mw / Mn) of 2.1, and stereoregularity (mesopentad fraction). : Mmmm) was 71.6 mol%, and the melting point (Tm-D) was 70.11 ° C.

Production Example 4 (Polyoctene-1 polymerization)
To a heat-dried 1 liter autoclave, 400 ml of octene-1, 0.4 mmol of triisobutylaluminum, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis ( 5-micromol of 3-trimethylsilylmethylindenyl) zirconium dichloride and 15 micromol of dimethylanilinium tetrakispentafluorophenylborate were added, and 0.05 MPa of hydrogen was further introduced. Polymerization was carried out at 85 ° C. for 120 minutes. After completion of the polymerization reaction, 5 ml of ethanol was added to stop the reaction, and the reaction product was dried at 110 ° C. under reduced pressure to obtain 80 g of polyoctene-1.
The intrinsic viscosity [η] of the obtained polyoctene-1 was 0.17 deciliter / g, the polypropylene-converted weight average molecular weight (Mw) measured by GPC method was 35,900, and the molecular weight distribution (Mw / Mn) was 2.3. The stereoregularity (mesopentad fraction: mmmm) was 43.1 mol%, and the melting point (Tm-D) measured by DSC was not observed.

Example 1 (Silane modification of polybutene-1)
60 g of polybutene-1 obtained in Production Example 2 was charged into a 0.5-liter Separa flask equipped with a nitrogen introduction tube, a Dimroth tube, and a stirrer, and heated to 130 ° C. using a bath temperature in a nitrogen atmosphere. After the temperature was raised, the contents were melted and stirring was started. Thereafter, 0.6 g of trimethoxyvinylsilane (5.0 g) and Perhexa 25B (manufactured by NOF Corporation) were added, and the temperature was raised to 150 ° C., and further heated to 160 ° C. and stirred for 30 minutes. After lowering the temperature, the obtained reaction product was dried under heating under reduced pressure to obtain the desired product.
The intrinsic viscosity [η] of the obtained silane-modified polymer is 0.17 deciliter / g, the weight average molecular weight (Mw) is 19,700, Mn is 8,500, and the molecular weight distribution (Mw / Mn) is 2.3. The stereoregularity (mesopentad fraction: mmmm) was 64.7 mol%, the melting point (Tm-D) was 64.5 ° C., and the half crystallization time was 85 minutes. The alkoxysilyl group concentration was 1.8% by mass, and the number of terminal unsaturated groups per molecule was 0.65.
Further, when the dynamic viscoelasticity of the obtained polymer was measured, the Tan δ at 0 ° C. was 0.20, and the Tan δ at 60 ° C. was 0.06.

Example 2 (Silane modification of polybutene-1)
In Example 1, it replaced with polybutene-1 of manufacture example 2, and carried out similarly to example 1 except having changed to polybutene-1 of manufacture example 3.
The intrinsic viscosity [η] of the obtained silane-modified polymer was 0.33 deciliter / g, the weight average molecular weight (Mw) was 37,900, Mn was 18,100, and the molecular weight distribution (Mw / Mn) was 2.1. The stereoregularity (mesopentad fraction: mmmm) was 71.5 mol%, the melting point (Tm-D) was 67.5 ° C., and the half-crystallization time was 68 minutes. The alkoxysilyl group concentration was 5.1% by mass, and the number of terminal unsaturated groups per molecule was 0.40.
Further, when the dynamic viscoelasticity of the obtained polymer was measured, the Tan δ at 0 ° C. was 0.22, and the Tan δ at 60 ° C. was 0.05.

Example 3 (Silane modification of polyoctene-1)
In Example 1, it replaced with polybutene-1 of manufacture example 2, and carried out similarly to example 1 except having changed to polyoctene-1 of manufacture example 4.
The intrinsic viscosity [η] of the obtained silane-modified polymer is 0.17 deciliter / g, the weight average molecular weight (Mw) is 45,400, Mn is 18,600, and the molecular weight distribution (Mw / Mn) is 2.4. The stereoregularity (mesopentad fraction: mmmm) was 43.1 mol%, the melting point (Tm-D) and the half crystallization time were not observed. The alkoxysilyl group concentration was 2.7% by mass, and the number of terminal unsaturated groups per molecule was 0.83.
Since this material is liquid at room temperature, 0.04 g of dibutyltin dilaurate was added to 2 g of this material and stirred, and then cured using a predetermined mold at 25 ° C. and 50% humidity for 24 hours. .
When the dynamic viscoelasticity of the obtained molded product was measured, Tan δ at 0 ° C. was 0.14, and Tan δ at 60 ° C. was 0.05.

Example 4 (Preparation of resin composition)
SBS (Clayton B1102JSZ) 40.0 g and silica (Merck Silica gel 60) 8.0 g, silane-modified polymer 3.24 g obtained in Example 2, sulfur 0.64 g, process oil (Idemitsu Kosan Co., Ltd.) PS-32) manufactured by company was put into a 300 mL mayonnaise bottle, melted at 190 ° C. in an oil bath, and stirred for 5 minutes with a three-one motor and a stirring blade to obtain a resin composition.

Comparative Production Example 1 (Polybutene-1 polymerization)
21 g of polybutene-1 was obtained in the same manner as in Production Example 2 except that the polymerization temperature was changed to 70 ° C. in Production Example 2 and changed to 50 ° C. and hydrogen to 0.02 MPa and 0.1 MPa. .
The resulting polybutene-1 had an intrinsic viscosity [η] of 0.61 deciliter / g, a weight average molecular weight (Mw) of 73,800, a molecular weight distribution (Mw / Mn) of 2.1, and stereoregularity (mesopentad fraction). : Mmmm) was 72.8 mol%, and the melting point (Tm-D) was 71.2 ° C.

Comparative Example 1 (Silane modification of polybutene-1)
17 g of polybutene-1 obtained in Comparative Production Example 1 was introduced into a 0.5 liter Separa flask equipped with a nitrogen introduction tube, a Dimroth tube, and a stirrer, and heated to 130 ° C. using a bath temperature in a nitrogen atmosphere. After the temperature was raised, stirring was started after the contents were melted. Thereafter, 0.14 g of trimethoxyvinylsilane (1.4 g) and perhexa 25B (manufactured by NOF Corporation) were added, and the temperature was raised to 150 ° C., and further raised to 160 ° C. and stirred for 30 minutes. After lowering the temperature, the obtained reaction product was dried under heating under reduced pressure to obtain the desired product.
The resulting silane-modified polymer has an intrinsic viscosity [η] of 0.62 deciliter / g, a weight average molecular weight (Mw) of 74,700, Mn of 32,200, and a molecular weight distribution (Mw / Mn) of 2.3. The stereoregularity (mesopentad fraction: mmmm) was 72.8 mol%, the melting point (Tm-D) was 71.0 ° C., and the half-crystallization time was 80 minutes. The alkoxysilyl group concentration was 5.1% by mass, and the number of terminal unsaturated groups per molecule was 0.20.
Moreover, when the dynamic viscoelasticity of the obtained silane modified polymer was measured, Tan δ at 0 ° C. was 0.21, and Tan δ at 60 ° C. was 0.06.

Comparative Example 2 (Preparation of resin composition)
In Example 4, a resin composition was obtained in the same manner as in Example 4 except that the silane-modified polymer obtained in Comparative Example 1 was used instead of the silane-modified polymer obtained in Example 2. It was.

Comparative Example 3 (Preparation of resin composition)
In Example 4, a resin composition was obtained in the same manner as in Example 4 except that the silane-modified polymer obtained in Example 2 was not used.

<Evaluation of resin composition>
Using the resin compositions obtained in Example 4 and Comparative Examples 2 and 3, press plates of 10 mm × 30 mm × 1 mm were respectively produced with a press machine at a melting temperature of 230 ° C. The obtained press plate was cut into prisms about 1 to 2 mm in length and width and about 3 mm in height, immersed in liquid nitrogen for 15 minutes or more, then the sample was taken out and immediately frozen with a razor. After drying at room temperature, conductive treatment by Os coating is performed, and the frozen section of the press plate is subjected to an accelerating voltage of 15 kV and reflected electron composition image using a scanning electron microscope (SEM: JSM-6480LA manufactured by JEOL Ltd.). The dispersion state of silica in the cross section of the press plate was evaluated (FIG. 1).

FIG. 1 shows an SEM photograph of a cross section of a sample from (a) the resin composition of Example 4, (b) the resin composition of Comparative Example 2, and (c) the resin composition of Comparative Example 3.
From FIG. 1, silane coupling containing a large amount of alkoxysilane and unsaturated groups compared to the case (b) where a silane coupling agent having few unsaturated groups is used and the case (c) where no silane coupling agent is added. When the agent is used, it can be seen that the dispersibility of the silica in (a) is high (white portion is silica).

  The above results are summarized in Table 1.

  The modified olefin polymer of the present invention can be suitably used mainly for high silica dispersion in a tire rubber composition.

Claims (5)

A tire rubber composition comprising a modified olefin polymer , a diene rubber polymer, silica and sulfur satisfying the following (a) to (g).
(A) The intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is 0.01 to 2.5 dL / g.
(B) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the observed peak is not observed or is 0-100 ° C.
(C) The half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed.
(D) The weight average molecular weight (Mw) is 1,000 to 500,000.
(E) The alkoxysilyl group concentration is 0.01 to 50% by mass.
(F) The number of terminal unsaturated groups per molecule is 0.4 or more.
(G) 50 mol% or more of the olefin monomers constituting the polymer are one or more monomers selected from α-olefins having 3 to 28 carbon atoms. The tire rubber composition according to claim 1, wherein the modified olefin polymer has a Tan δ at 0 ° C of greater than 0.1 and a Tan δ at 60 ° C of less than 0.1 of the dynamic viscoelasticity when solid. The tire rubber composition according to claim 1 or 2, wherein the modified olefin polymer has a weight average molecular weight (Mw) of 1,000 to 60,000. It was prepared using a metallocene catalyst α- olefin polymer a radical initiator, and a silane group and an ethylenically unsaturated group-modified olefin polymers obtained I rows modification treatment with a monomer having a diene rubber polymer The manufacturing method of the rubber composition for tires as described in any one of Claims 1-3 which mixes silica and sulfur . The metallocene-based catalyst reacts with (i) the transition metal compound represented by the following general formula (I), and (ii) (ii-1) the transition metal compound of the component (i) or a derivative thereof, to give an ionic The manufacturing method of the rubber composition for tires of Claim 4 containing the component chosen from the compound and (ii-2) aluminoxane which can form a complex.
[In the formula, M represents a group 3-10 of the periodic table or a lanthanoid series metal element, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, respectively. A ligand selected from a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure via A ¹ and A ² In addition, they may be the same or different from each other, X represents a σ-bonded ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , E ² or Y may be cross-linked. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group _{, -O -, - CO -,} - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]