阅读说明：本技术 改性共轭二烯系聚合物、聚合物组合物以及橡胶组合物 (Modified conjugated diene polymer, polymer composition and rubber composition ) 是由 长谷部公一 铃木僚 仲二见裕美 于 2018-04-26 设计创作，主要内容包括：本发明的改性共轭二烯系聚合物的重均分子量为20×10<Sup>4</Sup>以上300×10<Sup>4</Sup>以下,分子量分布Mw/Mn为1.6以上、4.0以下,相对于共轭二烯系聚合物的总量的改性率为30质量％以上80质量％以下,GPC(凝胶渗透色谱法)中的分子量为100万以上500万以下的成分为5质量％以上50质量％以下,上述分子量为100万以上500万以下的成分的改性率为90质量％以上100质量％以下。(The weight average molecular weight of modified conjugated diene polymer of the invention is 20 × 10 4 Above 300 × 10 4 Below, molecular weight distribution mw/mn is 1.6 or more, 4.0 or less, the degree of modification of total amount relative to conjugated diene polymer is 30 mass % or more, 80 mass % or less, molecular weight in GPC (gel permeation chromatography) is that 1,000,000 or more 500 ten thousand ingredients below are 5 mass % or more, 50 mass % hereinafter, the degree of modification that above-mentioned molecular weight is 1,000,000 or more 500 ten thousand ingredients below is 90 mass % or more, 100 mass % or less.)

1. a kind of modified conjugated diene polymer, wherein

Weight average molecular weight is 20 × 10⁴Above 300 × 10⁴Hereinafter,

Molecular weight distribution mw/mn be 1.6 or more, 4.0 hereinafter,

The degree of modification of total amount relative to conjugated diene polymer be 30 mass % or more, 80 mass % hereinafter,

Molecular weight in gel permeation chromatography GPC is that 1,000,000 or more 500 ten thousand ingredients below are 5 mass % or more, 50 matter Measure % hereinafter,

The molecular weight is that the degree of modification of 1,000,000 or more 500 ten thousand ingredients below is 90 mass % or more, 100 mass % or less.

2. modified conjugated diene polymer as described in claim 1, wherein summit in GPC or there are a plurality of peaks In the case where the maximum summit of molecular weight molecular weight constituent degree of modification be modified conjugated diene polymer entirety modification 1.10 times or more of rate.

3. modified conjugated diene polymer as claimed in claim 1 or 2, wherein molecular weight is the molecule of the summit in GPC Amount 1/2 or there are a plurality of peaks in the case where for the maximum summit of molecular weight molecular weight 1/2 ingredient degree of modification It is 1/2 or less the degree of modification of modified conjugated diene polymer entirety.

4. modified conjugated diene polymer according to any one of claims 1 to 3, wherein

Mw/Mn in GPC be 2.0 or more 4.0 hereinafter,

Contraction factor g ' is 0.64 or more 1.00 or less.

5. modified conjugated diene polymer as described in any one of claims 1 to 4, wherein

Modified conjugated diene polymer contains the nitrogen and silicon of respectively 3 mass ppm or more,

Nitrogen is 1.1 more than and less than 10 relative to molar ratio, that is, nitrogen/silicon of silicon.

6. modified conjugated diene polymer as described in any one of claims 1 to 4, wherein

Modified conjugated diene polymer contains the nitrogen and silicon of respectively 3 mass ppm or more,

Nitrogen is 0.1 more than and less than 0.9 relative to molar ratio, that is, nitrogen/silicon of silicon.

7. a kind of polymer composition contains the modified conjugation according to any one of claims 1 to 6 of 10 mass % or more Diene copolymers.

8. a kind of rubber composition, it includes:

100 mass parts of rubber-like polymer, the rubber-like polymer contain any in the claim 1~6 of 10 mass % or more Modified conjugated diene copolymer described in, and

5~150 mass parts of filler.

Technical field

The present invention relates to modified conjugated diene polymer, polymer composition and rubber compositions.

Background technique

In recent years, the lower fuel consumption of automobile is required to improve, it is desirable that the wheel to automobile tyre, particularly with ground face contact Material used in tire tread is improved.All the time, iing is required that develop that rolling resistance is small, has low magnetic hystersis loss The material of property.

In addition, needing to reduce the thickness of tire face to mitigate the weight of tire, the material that abrasion performance is high is also required Material.

On the other hand, from safety aspect, material requirements anti-slippery used in tire tread it is excellent and With practical sufficient destruction characteristic.

As the such desired material of reply, there are include the enhancements such as rubber-like polymer and carbon black, silica The rubber material of filler.When using the rubber material comprising silica, low magnetic hystersis loss and anti-slippery can be realized Balanced improve.In addition following trials has also been carried out: by leading in the molecular end portion of the high rubber-like polymer of motility Enter and silica is affinity or reactive functional group, thus improve the dispersibility of the silica in rubber-like polymer, And then the motility by reducing the molecular end portion of rubber-like polymer in conjunction with silicon oxide particle, reduce magnetic hystersis loss.

For example, proposed in patent document 1 and 2 make ring type aza-silicon cycle compound and polymer active end reaction and Functionalized polymer is carried out.

In addition, proposing in patent document 3 makes polymer active end and multi-functional silane compound through coupling reaction Made of diene series rubber.

Summary of the invention

Problems to be solved by the invention

But there is hydrophobic surface this point relative to carbon black, silica has hydrophilic surface, the silica It is low with the conjugation compatibility of diene series rubber, have the shortcomings that the bad dispersibility compared with carbon black.Therefore, silica conduct is being used In the case where filler, in order to assign silica and the combination being conjugated between diene series rubber, improve dispersibility, need in addition to contain There is silane coupling agent etc..

In addition, being imported with and the functional group with high reactivity of silica about the molecular end in conjugated diene rubber Material, with following problems: being reacted in compounding procedure with silicon oxide particle, since the viscosity of rubber composition rises And be difficult to be kneaded, it is easy to happen rough surface when piece being either made after mixing or piece is easily broken off, processes sexual orientation In deterioration.

In addition, the material for having imported functional group have it is easy to attach in the metal surface of mold etc. the problem of.In turn, it is inciting somebody to action After sulfide is made in such material, after being especially formed into the sulfide comprising inorganic fillers such as silica, having cannot get The problem of sufficient abrasion performance.

Therefore, the purpose of the present invention is to provide a kind of modified conjugated diene polymer, can be obtained processing when and It is low with the adhesion of metal surface when vulcanization, be made after sulfide and used with high abrasion resistance, fuel-efficient consumption also excellent tire Rubber composition.

Means for solving the problems

The present inventor has made intensive studies to solve the project of the above-mentioned prior art, as a result, it has been found that, following modifications are total Yoke diene polymer is able to solve the project of the above-mentioned prior art, has thus completed the present invention, the modified conjugated diene Polymer is to have imported in polymer molecule and filler is affinity or the modified conjugated diene of reactive functional group Based polymer, weight average molecular weight and molecular weight distribution are particular range, have the degree of modification of prescribed limit, and are being based on In the Molecular weight plots of GPC (gel permeation chromatography), molecular weight is that the content of 1,000,000 or more 500 ten thousand ingredients below is special Determine range, and the degree of modification of the ingredient is particular range.

That is, the present invention is as described below.

[1]

A kind of modified conjugated diene polymer, in the polymer,

Weight average molecular weight is 20 × 10⁴Above 300 × 10⁴Hereinafter,

Molecular weight distribution mw/mn be 1.6 or more, 4.0 hereinafter,

The degree of modification of total amount relative to conjugated diene polymer be 30 mass % or more, 80 mass % hereinafter,

Molecular weight in GPC (gel permeation chromatography) is that 1,000,000 or more 500 ten thousand ingredients below are 5 mass % or more 50 mass % hereinafter,

Above-mentioned molecular weight be the degree of modification of 1,000,000 or more 500 ten thousand ingredients below be 90 mass % or more, 100 mass % with Under.

[2]

The modified conjugated diene polymer as described in [1], wherein summit in GPC or there are a plurality of peaks In the case of the maximum summit of molecular weight molecular weight constituent degree of modification be modified conjugated diene polymer entirety degree of modification 1.10 times or more.

[3]

The modified conjugated diene polymer as described in [1] or [2], wherein molecular weight is the molecule of the summit in GPC Amount 1/2 or there are a plurality of peaks in the case where for the maximum summit of molecular weight molecular weight 1/2 ingredient degree of modification It is 1/2 or less the degree of modification of modified conjugated diene polymer entirety.

[4]

Modified conjugated diene polymer as described in any one of [1]~[3], wherein

Mw/Mn in GPC be 2.0 or more 4.0 hereinafter,

Contraction factor g ' is 0.64 or more 1.00 or less.

[5]

Modified conjugated diene polymer as described in any one of [1]~[4], wherein

Modified conjugated diene polymer contains the nitrogen and silicon of respectively 3 mass ppm or more,

Nitrogen is 1.1 more than and less than 10 relative to the molar ratio (nitrogen/silicon) of silicon.

[6]

Modified conjugated diene polymer as described in any one of [1]~[4], wherein

Modified conjugated diene polymer contains the nitrogen and silicon of respectively 3 mass ppm or more,

Nitrogen is 0.1 more than and less than 0.9 relative to the molar ratio (nitrogen/silicon) of silicon.

[7]

A kind of polymer composition contains modified conjugation two described in any one of [1]~[6] of 10 mass % or more Alkene copolymer.

[8]

A kind of rubber composition, it includes:

100 mass parts of rubber-like polymer, the rubber-like polymer contain any in [1]~[6] of 10 mass % or more Modified conjugated diene copolymer described in, and

5~150 mass parts of filler.

The effect of invention

In accordance with the invention it is possible to provide a kind of modified conjugated diene polymer, can be obtained in processing and when vulcanization It is low with the adhesion of metal surface, be made after sulfide with high abrasion resistance, fuel-efficient consumption also excellent tyre rubber group Close object.

Specific embodiment

A specific embodiment of the invention (hereinafter referred to as " present embodiment ") is described in detail below.Below Embodiment is for illustrating illustration of the invention, it is not intended that limits the invention to content below.The present invention can be It suitably deforms in the range of its main points to implement.

[modified conjugated diene polymer]

In the modified conjugated diene polymer of present embodiment,

Weight average molecular weight is 20 × 10⁴Above 300 × 10⁴Hereinafter,

Molecular weight distribution mw/mn be 1.6 or more 4.0 hereinafter,

The degree of modification of total amount relative to conjugated diene polymer be 30 mass % or more, 80 mass % hereinafter,

Molecular weight in GPC (gel permeation chromatography) is that 1,000,000 or more 500 ten thousand ingredients below are 5 mass % or more 50 mass % hereinafter,

Above-mentioned molecular weight be the degree of modification of 1,000,000 or more 500 ten thousand ingredients below be 90 mass % or more, 100 mass % with Under.

(weight average molecular weight)

The weight average molecular weight of the modified conjugated diene polymer of present embodiment is 20 × 10⁴Above 300 × 10⁴Below, Preferably 40 × 10⁴Ten thousand or more 250 × 10⁴Below, 50 × 10 are more preferably⁴Above 200 × 10⁴Below.

By making weight average molecular weight 20 × 10⁴Above 300 × 10⁴Hereinafter, the excellent wear resistance after sulfide is made.

The weight average molecular weight of modified conjugated diene polymer can be by adjusting the monomer additive amount, poly- in polymerization process It closes the polymerizing conditions such as additive amount and the polymerization time of initiator and controls in above-mentioned numberical range.

The weight average molecular weight of modified conjugated diene polymer is measured by the method recorded in aftermentioned embodiment.

(molecular weight distribution)

In the modified conjugated diene polymer of present embodiment, by weight average molecular weight (Mw) relative to number-average molecular weight The ratio between (Mn) molecular weight distribution mw/mn to indicate is 1.6 or more 4.0 or less.Molecular weight distribution is the modified conjugation of the range The polymer phase ratio of the molecular weight and degree of modification of diene polymer and equal extent has the processability when manufacturing sulfide More excellent tendency.Mw/Mn is preferably 1.8 or more 3.0 or less, more preferably 1.9 or more 2.5 or less.

The molecular weight distribution of modified conjugated diene polymer can by adjusting in polymerization process polymerization temperature and The polymerizing conditions such as polymerization time and control in above-mentioned numberical range, more preferably manufactured by continuous polymerization.

In addition, the modified conjugated diene polymer of present embodiment includes below point of 5 mass % or more, 50 mass % Son amount is 1,000,000 or more 500 ten thousand modified conjugated diene polymer (hereinafter sometimes referred to as " specific high molecular weight below Ingredient ", " high molecular weight components ").There is after sulfide is made abrasion performance more excellent tendency as a result,.It is above-mentioned specific The content of high molecular weight components be preferably 6 mass % or more, 45 mass % or less, more preferably 7 mass % or more, 40 mass % with Under.

The molecular weight distribution of modified conjugated diene polymer about present embodiment, the Molecular weight plots based on GPC The shape on preferably unimodal (mountain) or be trapezoidal or even peak type shape in the case where a plurality of peaks.The even shape of peak type Shape refers to that the height of the lowest part between peak and peak is 50% or more shape of the peak height of two sides.With such molecule The modified conjugated diene polymer of amount distribution has the tendency of the balancing good of low magnetic hystersis loss and anti-slippery.

The content of above-mentioned such above-mentioned specific high molecular weight components is in 5 mass % or more, 50 mass % in order to obtain The modified conjugated diene polymer of range below, such as adjustable aftermentioned organo monolithium compounds cause as polymerization The dosage of agent, in addition, in the polymerization process described below, in any polymerization methods in continous way, intermittent, selection, which has, to stop The method for staying Annual distribution, the method for namely making the Annual distribution of growth response broaden are effective.

It as the specific method in continous way, can enumerate: using the tank reactor with blender and be used as benefit The method of the back mixed flow reactor of the form mixed with blender fierceness, the method for being preferably used as being thoroughly mixed type reactor, The dose location of polymerization initiator is set as monomer inlet or sets by the method that is recycled in tube-type reactor to a part The method of the entrance of other polymerizations on the way near it and the method that groove profile and tube-type reactor are applied in combination.

According to these methods, it is capable of increasing residence time destribution, the component of polymer for keeping the residence time long becomes macromolecule Measure ingredient.

In addition, as the specific method in intermittent, for example, by polymerization initiator from polymerization starting The method being continuously or discontinuously fed during polymerization on the way.

This method is following method: having carried out polymerization from the time of the initiation for initially loading polymerization initiator polymerize Polymer is high molecular weight components, and molecular weight differences are generated between the polymer polymerizeing with causing later.More specifically, if according to It is continuous into monomer for the mode between such as 0%~95% with conversion ratio with the amount of the comparable polymerization initiator of target molecular weight Feed, then molecular weight distribution can be made by, which tending to, has obtained widened polymer.

By using the above method, the activity ratio of the reactive terminal of the conjugated diene polymer before reaction process is inclined to In increasing, it is intended to the high modified conjugated diene polymer of Conjugate ratio, i.e. degree of modification after being coupled.

, it is preferable to use what the tank reactor with blender and being used as was vigorously mixed using blender in these methods The method of the back mixed flow reactor of form.

It should be noted that " molecular weight " in this specification refers to the mark obtained using GPC (gel permeation chromatography) Quasi- polystyrene conversion molecular weight.

Number-average molecular weight, weight average molecular weight, molecular weight distribution can be surveyed by the method recorded in aftermentioned embodiment It is fixed.

(degree of modification)

Degree of modification of the modified conjugated diene polymer of present embodiment relative to the total amount of conjugated diene polymer For 30 mass % or more, 80 mass % or less, preferably 40 mass % or more, 75 mass % or less, more preferably 50 mass % with Upper 70 mass % or less.

In general, there is low magnetic after sulfide is made in the case where the degree of modification of modified conjugated diene polymer is high The tendency of the balancing good of stagnant lossy and anti-slippery.On the other hand, have processability deterioration, particularly with metal surface Adhesion improves and makes the tendency of workability deterioration.

It is speculated that due to, with it is easy to attach in the low molecular weight compositions of metal surface compared with, with high degree of modification height The interaction of molecular weight constituent and metal surface is bigger.

Therefore, in present embodiment, designed in the following manner: make the 30 mass % of lower limit of degree of modification with On, obtain the effect because of the balance of low magnetic hystersis loss and anti-slippery brought by modification；On the other hand, by the upper of degree of modification Limit is set as 80 mass % or less to inhibit the deterioration of processability；And as described below, by controlling specified molecular weight ingredient Degree of modification and inhibit polymer in the attachment of metal surface.

Degree of modification is that will have in polymer molecule and filler is affinity or the particular functional of bonding reaction The component of polymer of group relative to the total amount of conjugated diene polymer content with quality % come the numerical value that indicates.

As with filler is affinity or the particular functional group of bonding reaction, can preferably enumerate have comprising The functional group of the functional group of nitrogen-atoms, silicon atom, oxygen atom.

From make comprising present embodiment modified conjugated diene polymer rubber-like polymer combined with filler and At rubber composition in low magnetic hystersis loss and anti-slippery balancing good in terms of set out, the modification of present embodiment Conjugated diene polymer is preferably the modified conjugated diene polymer for having above-mentioned functional group in the end of polymer.Such as Can enumerate polymerization initiating terminal be bonded with the functional group with nitrogen-atoms polymer and/or terminate end utilize comprising Nitrogen-atoms, silicon atom, oxygen atom the modified conjugated diene polymer that is modified of functional group.

Degree of modification can be surveyed by that can separate the chromatography of the altered contents containing functional group and non-modified ingredient It is fixed.As the method for using the chromatography, can enumerate use the silica isopolarity substance that will adsorb particular functional group as The internal standard of non-adsorbed ingredient is used for comparison to carry out quantitative method by the gel permeation chromatography column of filler.

More specifically, the sample solution comprising sample and low molecular weight internal standard polystyrene is coagulated using polystyrene Rubber column gel column is measured, and is determined by the difference of obtained chromatogram and the chromatogram measured using silica bitt in oxygen Adsorbance on SiClx column, calculates degree of modification.

Further specifically, degree of modification can be measured by the method recorded in embodiment.

The degree of modification of modified conjugated diene polymer can be by adjusting the polymerization temperature in polymerization process and when polymerization Between the modified conditions such as equal polymerizing conditions and modifying agent additive amount in modified-reaction process and modification time and control above-mentioned Numberical range.

(degree of modification of specific high molecular weight ingredient)

The present inventor is had found by measuring the degree of modification in each molecular weight region in the Molecular weight plots based on GPC Degree of modification is different according to polymer in each molecular weight region.

In addition, it is found that the modified conjugated diene polymer with the uniform same degree of modification of the degree of modification of each molecular weight region It compares, the modified diene based polymer of the more non-uniform specific structure of the degree of modification of each molecular weight region, particularly above-mentioned The modified conjugated diene polymer that the degree of modification of specific high molecular weight components is high is excellent in specific aspect of performance.

In the modified conjugated diene polymer of present embodiment, molecular weight in GPC is 1,000,000 or more 500 ten thousand or less High molecular weight components degree of modification be 90 mass % or more, 100 mass % or less.Preferably 95 mass % or more, it is more preferably 98 mass % or more.

In the high modified conjugated diene polymer of the degree of modification of the high molecular weight components, pass through the macromolecule of high degree of modification The interaction for measuring ingredient and silica, shows high abrasion resistance after sulfide is made.

The high modified conjugated diene polymer of the degree of modification of the high molecular weight components can be obtained by continuous polymerization.As Specific method in continuous polymerization can be enumerated: using the tank reactor with blender and be used as swashing using blender The method of the back mixed flow reactor of strong mixed form is preferably used as being thoroughly mixed the method for type reactor, react in cast The dose location of polymerization initiator is set as monomer inlet or other near it by the method that is recycled in device to a part The method of the entrance of polymerization on the way and the method that groove profile and tube-type reactor are applied in combination, are preferably stirred using band The method for being thoroughly mixed type reactor that the tank reactor of machine is vigorously mixed using blender.

It is thought that can inhibit high in the case where not reducing the monomer concentration of polymerizer near exit by these methods The generation of the deactivated polymer of molecular weight, thus make the high molecular weight below of molecular weight 1,000,000 or more 5,000,000 in GPC at The degree of modification divided is 90 mass % or more, 100 mass % or less.

The degree of modification of each specific molecular weight constituent can by can separate the altered contents containing functional group and The chromatography of non-modified ingredient is measured.

As the method for using the chromatography, can enumerate using the silica isopolarity substance that will adsorb particular functional group As the gel permeation chromatography column of filler, the internal standard of non-adsorbed ingredient is used for comparison to carry out quantitative method.

More specifically, the degree of modification of each molecular weight constituent is obtained by following methods: will include sample and low point The sample solution of son amount internal standard polystyrene is measured using polystyrene gel column, by obtained chromatogram and utilization The difference of every kind of molecular weight constituent in the chromatogram that silica bitt measures determines the adsorbance on silicon oxide column. Further specifically, degree of modification can be measured by the method recorded in aftermentioned embodiment.

(degree of modification of summit)

In present embodiment, summit in GPC curve or there are a plurality of peaks in the case where the maximum peak of molecular weight The degree of modification of the molecular weight constituent of summit is preferably 1.10 times or more of the degree of modification of modified conjugated diene polymer entirety, more Preferably 1.15 times or more, further preferably 1.20 times or more.

The degree of modification of the molecular weight constituent of the summit is higher than the modification of the degree of modification of modified conjugated diene polymer entirety Conjugated diene polymer has the tendency that the excellent wear resistance after sulfide is made.

In order to make summit in GPC curve or there are a plurality of peaks in the case where the maximum peak of molecular weight summit The degree of modification of molecular weight constituent is 1.10 times or more of the degree of modification of modified conjugated diene polymer entirety, will imported into polymerization Polymerization terminator included in monomer and solvent in reactor, the impurity to work as chain-transferring agent amount be adjusted so as to compare It is usually more effective.

(degree of modification of low molecular weight compositions)

In the modified conjugated diene polymer of present embodiment, there are molecules in the case where a peak in GPC curve Amount be the peak summit 1/2 or there are a plurality of peaks in the case where be the maximum summit of molecular weight molecular weight 1/2 The degree of modification of ingredient (hereinafter sometimes referred to as " low molecular weight compositions "), which is preferably that modified conjugated diene polymer is whole, to be changed Property rate 1/2 or less, more preferably 0.1 times or more 0.4 times or less of the bulk modified rate of modified conjugated diene polymer.It is this In the case of, the entanglement of low molecular weight compositions reduces, therefore the modified conjugation two that the mobility that can obtain rubber composition is excellent Alkene based polymer.

Especially for the low rubber of adhesion when obtaining excellent abrasion performance and mobility, processing on the metal surface Composition, the degree of modification of above-mentioned low molecular weight compositions are preferably 0.3 times of the degree of modification of modified conjugated diene polymer entirety Above 0.5 times or less.

The degree of modification of the above-mentioned low molecular weight compositions of present embodiment, which is that modified conjugated diene polymer is whole, to be changed Property rate 1/2 modified conjugated diene polymer below can be obtained by following methods: carry out high temperature polymerization method, increase After adding the stage for the monomer conversion for realizing 98% or more polymerization on the way stopping reaction method, by polymerization system Interior progress Forced Mixing and seek the widened method of residence time destribution, utilize 2 based on the coupling agent with modified group The method etc. of coupling reaction more than molecule.

Modified conjugated diene polymer according to the present embodiment exists when having obtained to play in processing with vulcanization Adhesion on metal surface is low and both at first sight reverse effects of high abrasion resistance are shown after sulfide is made Modified conjugated diene polymer.

The mechanism for obtaining such modified conjugated diene polymer is not necessarily clear but as follows by inference.

There is the polar group comprising nitrogen, phosphorus, oxygen etc. generally, due to modifying residues, thus it is mutual with metal surface Effect is big.In the case where the degree of modification of above-mentioned low molecular weight compositions is high, there is low point for being largely bonded with modifying residues Son amount ingredient, when being kneaded, the low molecular weight compositions with modifying residues are liable to stick to the metallic surfaces such as roller.In metal Surface be attached with low molecular weight compositions in the case where, entanglement effect of the low molecular weight compositions between polymer is small, therefore poly- Object is closed to be liable to stick on metal.In contrast, thus it is speculated that be set as by the degree of modification of modified conjugated diene polymer entirety The degree of modification of above-mentioned high molecular weight components is set as 90 mass % or more simultaneously by 30 mass % or more, 80 mass % range below In 100 mass % situations below, there can be the high molecular weight components for being largely bonded with modifying residues, have when being kneaded The high molecular weight components of modifying residues are liable to stick to the metallic surfaces such as roller, but since the entanglement effect of strand increases, Thus it is wrapped on macromolecular chain and is not easy to remain in metal surface.

(composition of modified conjugated diene polymer)

The modified conjugated diene polymer of present embodiment preferably in polymerization initiating terminal and/or stops end bonding There is the modified conjugated diene polymer of modifying residues (its have with filler is affinity or reactive functional group).

That is, the modified conjugated diene polymer of present embodiment is preferably by modifying residues and conjugation with functional group Diene polymer chain is constituted.

<modifying residues>

Modifying residues in the modified conjugated diene polymer of present embodiment are to be bonded in conjugated diene polymerization The structural unit of modified conjugated diene polymer on object chain is e.g. made conjugated diene polymer and is changed by aftermentioned Property agent reaction and generate the structural unit from modifying agent.

Modifying residues have and filler is affinity or the particular functional group of bonding reaction.

The modified conjugated diene polymer of present embodiment is that the modification for being bonded with functional group in polymerization initiating terminal is total to In the case where yoke diene polymer, which can be caused by using the polymerization with functional group Agent carries out polymerization reaction and obtains.

<preferred embodiment about functional group>

As above-mentioned affinity with filler or bonding reaction functional group, can preferably enumerate comprising nitrogen original The functional group of son, silicon atom.

It is further preferred that the ratio between the molal quantity of the molal quantity of nitrogen-atoms relative to silicon atom, the i.e. molar ratio of N/Si are preferred It is 0.1~10.0, more preferably 0.2~7.0.

It is especially good with the compatibility of silicon oxide series filler when the molar ratio of N/Si is the range, use oxidation The magnetic hystersis loss of the rubber composition of silicon systems filler is small, and the rubber composition as low fuel consumption tire plays good property Energy.

As the functional group comprising silicon atom, it can enumerate but be not limited to such as methoxysilyl, (ethoxymethyl) silicon Alkyl, isopropoxysilyl group etc..

In addition, can enumerate but be not limited to such as secondary amine, tertiary amine groups as the functional group comprising nitrogen-atoms.

In addition, the modified conjugated diene polymer of present embodiment preferably has in polymer molecule comprising nitrogen original The modified conjugated diene polymer of the functional group of son.In this case, as the functional group comprising nitrogen-atoms, particularly preferred nitrogen Atom includes at least the functional group of the secondary amine of-NH- type.In this case, silicon oxide series filler and charcoal are used as filler The magnetic hystersis loss of black rubber composition is low, and the rubber composition as low fuel consumption tire plays good performance.

In the case where modifying residues have silicon atom, at least one preferably in silicon atom constitute carbon atom number be 1~ 20 alkoxysilyl or silanol group.Thus it can improve the dispersion of the filler in the case where rubber composition is made Property, the tendency with the raising of fuel-efficient consumption.

In the modified conjugated diene polymer of present embodiment, the ends of a plurality of conjugated diene polymer chains can be with With 1 silicon atom bonding.A silicon is bonded in alternatively, it is also possible to the end of conjugated diene polymer chain and alkoxy or hydroxyl On atom, as a result, this silicon atom may be constructed alkoxysilyl or silanol group.

(monomer for constituting conjugated diene polymer)

The conjugated diene polymer before modified of the modified conjugated diene polymer of present embodiment, which passes through, at least will Conjugated diene compound polymerization obtains, as desired by by conjugated diene compound and vinyl aromatic compound The two copolymerization obtains.

As conjugated diene compound, it is not particularly limited as long as the monomer for that can polymerize, preferably every 1 molecule packet Conjugated diene compound containing 4~12 carbon atoms more preferably includes the conjugated diene compound of 4~8 carbon atoms.As Such conjugated diene compound can be enumerated but be not limited to such as 1,3-butadiene, isoprene, 2,3- dimethyl -1,3- Butadiene, 1,3- pentadiene, 3- methyl-1,3-pentylene, 1,3- hexadiene, 1,3- heptadiene.Among these, obtained from industry Easiness in terms of set out, preferably 1,3-butadiene, isoprene.One kind can be only used alone in they, can also be by 2 kinds It shares above.

As vinyl aromatic compound, do not have as long as the monomer for that can be copolymerized with conjugated diene compound It is particularly limited to, preferably single-ethenyl aromatic compound.As single-ethenyl aromatic compound, it can enumerate but be not limited to Such as styrene, p-methylstyrene, α-methylstyrene, vinyl ethylbenzene, vinyl-dimethyl benzene, vinyl naphthalene, diphenyl Ethylene.Among these, from the easiness aspect that industry obtains, optimization styrene.One kind can be only used alone in they, It can also share two or more.

(preferred embodiment in the case where SBR)

The case where modified conjugated diene polymer of present embodiment is butadiene-styrene random copolymer (SBR) Under, bonding styrene amount is preferably the 5 mass % of mass %~50, and vinyl bonds resultant is preferably 10 mass of mass %~75 %. When for the range, the SBR that all purposes are also suitable for other than tire purposes can be industrially obtained.

Especially bonding styrene amount be 25 mass of mass %~45 %, vinyl bonds resultant is 18 matter of mass %~30 In the case where measuring %, it can be obtained that magnetic hystersis loss is small, rubber composition of excellent wear resistance.

In addition, bonding styrene amount is 18 mass of mass %~28, vinyl bonds resultant is 45 matter of mass %~65 In the case where measuring %, in rubber composition, can be obtained that magnetic hystersis loss is small, province of excellent strength made of natural rubber mixture Oil consumption rubber composition for tire.

It should be noted that bonding styrene amount is the quality % of the styrene in whole monomer components, vinyl bonding Amount is the quality % of the vinyl bonds synthesis point in butadiene component.

(glass transition temperature)

The glass transition temperature (Tg) of the modified conjugated diene polymer of present embodiment is modified conjugated diene The strand of polymer starts the temperature of rotary motion, has larger impact for fuel-efficient consumption and wetland adherence properties.

In the case where Tg is low, fuel-efficient consumption is good, and in the case where Tg high, wetland adherence properties are improved.

In the case where the modified conjugated diene polymer for saving oil consumption tire purposes, Tg is preferably -20 DEG C or more 0 DEG C or less.Thus wetland adherence properties, rigidity become extremely good.The modified conjugated diene polymer high-performance tire with And it is extremely useful in very-high performance tire.

In addition, in the modified conjugated diene polymer of present embodiment, can enumerate Tg be -50 DEG C more than and less than - 20 DEG C of polymer is as preferred other modes.Thus make fuel-efficient consumption and the balance of wetland adherence properties extremely excellent.This changes Property conjugated diene polymer is extremely useful in summer tire and Weatherable tyre.

In addition, in the modified conjugated diene polymer of present embodiment, can enumerate Tg be -70 DEG C more than and less than - 50 DEG C of polymer is as preferred other modes.Thus cryogenic property and abrasion performance become extremely good.Modification conjugation Diene polymer is used extremely useful in tire in winter.In addition, can be in order to improve abrasion performance and as various tire treads Compounded materials carry out using.

The Tg of the modified conjugated diene polymer of present embodiment can be measured according to ISO22768:2006.

(preferred embodiment of random SBR)

The case where modified conjugated diene polymer of present embodiment is butadiene-styrene random copolymer (SBR) Under, the ratio of optimization styrene unit individualism is more, and preferably long-chain is few.

Specifically, modified conjugated diene polymer be butadiene-styrene copolymer in the case where, using as The method (Polymer, 22,1721 (1981)) of Tanaka et al. and the known method decomposed based on ozone are by above-mentioned copolymerization In the case that object is decomposed and analyzed using GPC styrene link distribution, preferably with respect to styrene amount is all bonded, divide It is 5 mass % or less from the link styryl structures that styrene amount is 40 mass % or more, styrene chain is 8 or more.It is this In the case of, the rubber composition for province's oil consumption tire that magnetic hystersis loss is small, has excellent performance especially can be obtained.

(hydrogenating conjugated diene polymers)

About the modified conjugated diene polymer of present embodiment, can to the modified conjugated diene polymer or Conjugated diene polymer before modified implements the processing further hydrogenated in atent solvent.Thus, it is possible to by the whole of double bond Or a part is converted into saturated hydrocarbons.In this case, heat resistance, weatherability improve, production when can prevent from processing at high temperature Product deterioration, has the tendency that the movenent performance as rubber can be improved.In addition, thus can be sent out in the various uses such as mobile applications Shoot superior performance.

The hydrogenation ratio of unsaturated double-bond based on conjugated diene compound can arbitrarily be selected according to purpose, not limited especially It is fixed.In the case where using as sulfide, the double bond in preferably conjugated diene portion has part residual.From this viewpoint, two are conjugated The hydrogenation ratio in the conjugated diene portion in alkene based polymer is preferably 3.0 moles of % or more, 70 moles of % or less, more preferably 5.0 rubs You are 65 moles of % or less of % or more, further preferably 10 moles of % or more, 60 moles of % or less.Especially by by vinyl It selectively hydrogenates, the tendency improved with heat resistance and movenent performance.Hydrogenation ratio can use nuclear magnetic resonance device (NMR) and ask Out.

(oil extended polymer, Mooney viscosity)

The oil extended polymer added with filling oil can be made in the modified conjugated diene polymer of present embodiment.This reality The modified conjugated diene polymer for applying mode can be non-oil extended polymer, or oil extended polymer.

In addition, processability when manufacturing vulcanized rubber composition and the abrasion performance being made after sulfide in terms of go out Hair, the Mooney viscosity that the modified conjugated diene polymer of present embodiment is measured at 100 DEG C is preferably 20 or more 100 or less, More preferably 30 or more 80 or less.The Mooney viscosity of modified conjugated diene polymer can be by recording in aftermentioned embodiment Method is measured.

(nitrogen, silicone content)

In the modified conjugated diene copolymer of present embodiment, from improving fuel-efficient consumption aspect, nitrogen and silicon are each From content be preferably 3 mass ppm or more, more preferably 7 mass ppm or more, further preferably 10 mass ppm or more.

Think that the modified conjugated diene copolymer of present embodiment can carry out physics suction using nitrogen when being kneaded with filler It is attached, be chemically combined using silicon, by making the above-mentioned numberical range of nitrogen, silicone content, the excellent rubber of magnetic hystersis loss can be obtained Glue composition.

In the modified conjugated diene copolymer of present embodiment, the molar ratio of contained nitrogen and silicon be it is critically important, It can disperse silica aspect from when being kneaded with the short time, nitrogen is preferably 1.1 relative to the molar ratio (N/Si) of silicon More than and less than 10, more preferably 1.3 or more 7 or less, further preferably 1.5 or more 5 or less.

About the preferred reason for the molar ratio above range for making N/Si, it is assumed that due to the physical absorption ratio based on nitrogen The reaction speed of chemical bonding based on silicon faster, thus preferably make nitrogen relative to the molar ratio equimolar of silicon more than.

In addition, molar ratio (N/ of the nitrogen relative to silicon can be enumerated in the modified conjugated diene copolymer of present embodiment It Si is) 0.1 copolymer more than and less than 0.9 as other preferred embodiments.It can disperse oxygen when being kneaded as a result, with the short time SiClx.In this case, which is more preferably 0.2 or more 0.75 or less, further preferably 0.3 or more 0.6 or less.

About preferred nitrogen relative to silicon molar ratio be 0.1 more than and less than 0.9 the reasons why, it is assumed that due to be based on nitrogen Physical absorption it is more stronger than the combination of the chemical bonding based on silicon, thus preferably nitrogen relative to silicon molar ratio be less than etc. rub You.In this case, the content of silicon is preferably 7 mass ppm or more.

The molar ratio of the nitrogen of the modified conjugated diene copolymer of present embodiment and the content of silicon and nitrogen relative to silicon (nitrogen/silicon) can the type of modifying agent used in the modified-reaction by adjusting conjugated diene copolymer, dosage carry out Control.

For example, by using modifying agent corresponding with the content of desired nitrogen and silicon or raising with defined content Molar ratio of the nitrogen relative to silicon in modifying agent can be improved molar ratio of the nitrogen relative to silicon of modified conjugated diene copolymer.

(contraction factor)

In the modified conjugated diene polymer of present embodiment, the contraction factor measured using 3D-GPC can be enumerated (g ') be 0.86 or more 0.99 modified conjugated diene polymer below it is preferred that.

Contraction factor (g ') by making the modified conjugated diene polymer of present embodiment is above range, has and draws Stretch the tendency of excellent strength.

Contraction factor (g ') is the index of the branched structure of modified conjugated diene copolymer, and contraction factor (g ') is 0.86 Above 0.99 modified conjugated diene polymer below is that the branch number in the modified diene based polymer of 1 molecule is 3 Chain modified conjugated diene polymer below.In this case, contraction factor (g ') be more preferably 0.88 or more 0.99 or less, Further preferably 0.90 or more 0.98 or less.

As the method for obtaining the modified conjugated diene copolymer, such as following methods are effective: will have 3 The modifying agent of a following reflecting point reacted with reactive terminal using the total mole number relative to polymerization initiator as one third with On molal quantity be added, to obtain 3 branches modified conjugated diene copolymer below.

In addition, the contraction measured using 3D-GPC can be enumerated in the modified conjugated diene polymer of present embodiment The factor (g ') be 0.64 or more 1.00 polymer below it is preferred that.

Such modified conjugated diene polymer can reduce the viscosity of the rubber composition added with filler, have and add The excellent tendency of work.

Contraction factor (g ') is the index of the branched structure of modified conjugated diene copolymer, and contraction factor (g ') is 0.64 Above 1.00 modified conjugated diene polymer below is that the branch number in the modified conjugated diene polymer of 1 molecule is 6 branches modified conjugated diene polymer below.

As the method for obtaining the modified conjugated diene copolymer, such as following methods are effective: will have 6 with The modifying agent of the lower reflecting point reacted with reactive terminal is to be 1/6th or more relative to the total mole number of polymerization initiator Molal quantity is added, to obtain 6 branches modified conjugated diene copolymer below.

It should be noted that in the modified conjugated diene polymer of present embodiment, preferably above-mentioned contraction factor (g ') It is 2.0 or more 4.0 or less for 0.64 or more 1.00 or less the and Mw/Mn based on GPC.It is added with the combination of filler as a result, The viscosity of object has the tendency being greatly reduced, and the effect that processability significantly improves can be obtained.

In addition, the contraction measured using 3D-GPC can be enumerated in the modified conjugated diene polymer of present embodiment The factor (g ') be 0.30 polymer more than and less than 0.86 it is preferred that.

The viscosity for attaching the rubber composition of filler can be greatly reduced in such modified conjugated diene polymer, add Work is extremely excellent.

Contraction factor (g ') is the index of the branched structure of modified conjugated diene copolymer, and contraction factor (g ') is 0.30 Modified conjugated diene polymer more than and less than 0.86 is the branch number in the modified conjugated diene polymer of 1 molecule For modified conjugated diene polymers more than 4 branches.

As the method for obtaining the modified conjugated diene copolymer, such as following methods are effective: will have 4 The modifying agent of a above reflecting point reacted with reactive terminal using the total mole number relative to polymerization initiator as a quarter with Under molal quantity be added, to obtain the modified conjugated diene copolymer of 4 branches or more.

In addition, using the contraction factor (g ') of 3D-GPC measurement in the modified conjugated diene polymer of present embodiment Preferably 0.30 more than and less than 0.70.

Such modified conjugated diene polymer can further decrease the viscosity of the rubber composition added with filler, Processability is more excellent.

Contraction factor (g ') is the index of the branched structure of the modified conjugated diene copolymer, and contraction factor (g ') is 0.30 modified conjugated diene polymer more than and less than 0.70 is the branch in the modified conjugated diene polymer of 1 molecule Chain number is the modified conjugated diene polymer of 5 branches or more.

As the method for obtaining the modified conjugated diene copolymer, such as following methods are effective: will have 5 with Above with the modifying agent of the reflecting point of active reaction end to be 1/5th below relative to the total mole number of polymerization initiator Molal quantity is added, to obtain the modified conjugated diene copolymer of 5 branches or more.

(" the GPC- with viscosity detector is hereinafter also referred to as by the GPC- light scattering determining with viscosity detector Light scattering determining " or " 3D-GPC measurement ") and the contraction factor (g ') that determines is the modified conjugated diene polymer The index of branch number.For example, with the reduction of contraction factor (g '), the branch number of modified conjugated diene polymer (such as star The high molecular branch number of shape (also referred to as " the arm numbers of Regular Star Polymers ")) tend to increase.

In the case that the modified conjugated diene polymer equal to absolute molecular weight is compared, modified conjugated diene The more more then contraction factors (g ') of the branch of polymer are smaller, thus contraction factor (g ') in this case may be used as the degree of branching Index.

Contraction factor (g ') is measured using 3D-GPC measurement.By the relational expression of inherent viscosity and molecular weight ([η]= Constant (K, α) in KM α ([η]: inherent viscosity, M: molecular weight) is set as logK=-3.883, α=0.771, and input 1000~ The range of 20000000 molecular weight M makes standardized intrinsic viscosity [η]₀With the relationship of molecular weight M.

Relative to the standardized intrinsic viscosity [η]₀, the characteristic by the sample measured by 3D-GPC in each molecular weight M glues [η] is spent with inherent viscosity [η] relative to standardized intrinsic viscosity [η]₀Relationship form calculated at each molecular weight M [η]/ [η]₀, using its average value as contraction factor (g ').

More specifically, it can be measured by the method recorded in aftermentioned embodiment.

(preferred structure of modified conjugated diene polymer)

The modified conjugated diene polymer of present embodiment preferably by the following general formula (I) represented by.

[changing 1]

In above-mentioned formula (I), D₁Indicate diene polymer chain, R¹~R³It each independently represents singly-bound or carbon atom number is 1 ~20 alkylidene, R⁴And R⁷Each independently represent the alkyl that carbon atom number is 1~20, R⁵、R⁸And R⁹It each independently represents The alkyl that hydrogen atom or carbon atom number are 1~20, R⁶And R¹⁰Each independently represent the alkylidene that carbon atom number is 1~20, R¹¹ The alkyl that expression hydrogen atom or carbon atom number are 1~20.

M and x indicates that 1~3 integer, x≤m, p indicate that 1 or 2, y indicate that 1~3 integer, y≤(p+1), z indicate 1 or 2 Integer.

There are the D in the case where a plurality of₁、R¹~R¹¹, m, p, x, y and z it is respectively independent.

The integer of i expression 0~6, the integer of j expression 0~6, the integer of k expression 0~6, the integer that (i+j+k) is 1~10, The integer that ((x × i)+(y × j)+(z × k)) is 1~30.

A indicate carbon atom number be 1~20 alkyl or have select free oxygen atom, nitrogen-atoms, silicon atom, sulphur atom, At least one of the group of phosphorus atoms composition atom and the organic group for not having reactive hydrogen.Wherein, the feelings for being 1 at (i+j+k) Under condition, A can also be not present.Modified conjugated diene polymer has after sulfide is made by the structure with formula (I) The more excellent tendency of the balance and abrasion performance of low magnetic hystersis loss and anti-slippery.

In the modified conjugated diene polymer of present embodiment, it is preferred that in above-mentioned formula (I), A indicates the following general formula (II) any one of~(V).

[changing 2]

In formula (II), B¹Singly-bound or carbon atom number are indicated as 1~20 alkyl, the integer of a expression 1~10, there are plural numbers B in the case where a¹It is respectively independent.

[changing 3]

In formula (III), B²The alkyl that expression singly-bound or carbon atom number are 1~20, B³Indicate that carbon atom number is 1~20 alkane Base, a indicate 1~10 integer, be respectively present it is a plurality of in the case where B²And B³It is respectively independent.

[changing 4]

In formula (IV), B⁴Singly-bound or carbon atom number are indicated as 1~20 alkyl, the integer of a expression 1~10, there are plural numbers B in a situation⁴It is respectively independent.

[changing 5]

In formula (V), B⁵Singly-bound or carbon atom number are indicated as 1~20 alkyl, the integer of a expression 1~10, there are a plurality of In the case of B⁵It is respectively independent.There is the balance that the low magnetic hystersis loss after sulfide and anti-slippery is made and wear-resisting as a result, The more excellent tendency of consumption.In addition there is the tendency being easy to get on practical.

[manufacturing method of modified conjugated diene polymer]

The manufacturing method of the modified conjugated diene polymer of present embodiment preferably has following processes: polymerization process, Use organo monolithium compounds as polymerization initiator, will at least conjugated diene compound polymerize, and obtain conjugated diene polymerization Object；And modified-reaction process, react the conjugated diene polymer with modifying agent, which has and conjugated diene The connection group of the reactive terminal reaction of polymer, and then have and filler is affinity or the specific official of bonding reaction It can group.

(polymerization process)

In the preferred embodiment of the polymerization process of the manufacturing method of the modified diene based polymer of present embodiment, by organic list Lithium compound will at least conjugated diene compound polymerize as polymerization initiator, and obtain conjugated diene polymer.

In polymerization process, preferably by being polymerize based on the growth response that active anionic polymerization reacts, it can thus be concluded that To the conjugated diene polymer of active end, there is inclining for the modified diene based polymer that can obtain high degree of modification To.

The modified diene based polymer of present embodiment is in the Molecular weight plots based on GPC in each molecular weight region The modified diene based polymer of the non-uniform specific structure of degree of modification.

In the modified conjugated diene polymer of present embodiment, the molecular weight of GPC is 1,000,000 or more 500 ten thousand below The degree of modification of ingredient (high molecular weight components) is 90 mass % or more, 100 mass % or less.

In addition, the degree of modification of above-mentioned high molecular weight components is preferably the degree of modification of modified conjugated diene polymer entirety 1.10 more than again.

In addition, the degree of modification of above-mentioned low molecular weight compositions is preferably the degree of modification of modified conjugated diene polymer entirety 1/2 or less.

The degree of modification in such specified molecular weight region is that the modified conjugated diene polymer of particular modification rate passes through control It has made the stopping of growth response or the polymerization of chain tra nsfer and has obtained.

Specifically, can be manufactured by application following methods etc.: making the monomer importeding into polymer reactor and molten The polymerization terminator that includes in agent, the impurity to work as chain-transferring agent amount than usual more methods；At high temperature into The method of row polymerization；Increase the method for the stopping reaction of the polymerization of the monomer conversion based on 98% or more on the way；Or it utilizes The side of the degree of modification of high molecular weight components is improved based on coupling reactions more than 2 molecules of the coupling agent with modified group Method；Etc..

Amounting to from the impurity in above-mentioned aspect, used monomer component is preferably 50ppm~300ppm；About The content concn (quality) of the impurity such as allene class (allene), acetylene class, primary amine and secondary amine, allene class is preferably 20ppm Above, it is more preferably 30ppm or more, acetylene class is preferably 20ppm or more, more preferably 30ppm or more, primary amine and secondary amine to close Counting nitrogen content meter is preferably 5ppm or more.

As allene class, for example, allene, 1,2- butadiene.

As acetylene class, for example, ethyl acetylene, vinylacetylene.

As primary amine and secondary amine, for example, methylamine, dimethylamine.

In order to control stopping or the polymerization of chain tra nsfer of growth response, further preferably to polymerization temperature Control and monomer adding rate are controlled.Polymerization temperature be preferably carry out active anionic polymerization temperature, preferably 75 DEG C with Upper 110 DEG C or less.More preferably 80 DEG C or more 100 DEG C or less.

Additionally, it is preferred that by the conversion ratio of monomer entirety be 98% or more, preferably in the way of 99% or more and modifying agent into Row reaction.

Conjugated diene polymer obtained in polymerization process can be random copolymer, or block copolymer. In order to which rubber-like polymer is made in conjugated diene polymer, the monomer relative to conjugated diene polymer is whole, conjugation Diolefin compound it is preferable to use it is more than 40 mass %, more preferably use 55 mass % or more.

As random copolymer, can enumerate but be not limited to such as butadiene-isoprene random copolymer by 2 kinds with On conjugated diene compound constitute random copolymer, butadiene-styrene random copolymer, isoprene styrene without Copolymer, butadiene-isoprene-styrene random copolymer etc. are advised by conjugated diene and vinyl aromatic compound The random copolymer of composition.

Composition distribution as each monomer in co-polymer chain is not particularly limited, for example, close to statistics Progressive (gradient) random copolymer that the complete random copolymer randomly formed, composition on are distributed with progressive shape.Conjugation two The compositions such as the bonding scheme of alkene, i.e. Isosorbide-5-Nitrae-bonding, 1,2- bonding can be uniformly, be also possible to distribution.

As block copolymer, it can enumerate but be not limited to 2 type block copolymers being for example made of 2 blocks (two is embedding Section), the 3 type block copolymers (three block) that are made of 3 blocks, (four is embedding for 4 type block copolymers being made of 4 blocks Section).It can be the polymer being made of a kind of monomer, or by list of more than two kinds as the polymer for constituting 1 block The copolymer that body is constituted.For example, the polymer blocks being made of 1,3-butadiene are indicated with " B ", by 1,3-butadiene with it is different The copolymer of pentadiene indicates with " B/I ", the copolymer of 1,3- butadiene and styrene indicated with " B/S ", will be by styrene When the polymer blocks of composition are indicated with " S ", block copolymer is with 2 type block copolymer of B-B/I, 2 type block copolymerization of B-B/S Object, 2 type block copolymer of S-B, 3 type block copolymer of B-B/S-S, 3 type block copolymer of S-B-S, 4 type of S-B-S-B are embedding Section copolymer etc. indicates.

In above-mentioned formula, it is not absolutely required to clearly distinguish for each embedding section boundary.In addition, in 1 polymer blocks by two kinds In the case where the copolymer that monomer is constituted, each monomer in block can be uniformly distributed, or can also be distributed with progressive shape.

<polymerization initiator>

As polymerization initiator, organo monolithium compounds are preferably at least used.

As organo monolithium compounds, it can enumerate but be not limited to having for such as low molecular compound, solubilized oligomer Machine list lithium compound.In addition, in the bonding scheme of the organic group and the lithium, can be enumerated as organo monolithium compounds Such as compound, the compound with the bonding of nitrogen-lithium and with tin-lithium bonding compound closed with carbon-lithium bonds.

Organo monolithium compounds as polymerization initiator dosage preferably according to target conjugated diene polymer or modification The molecular weight of conjugated diene polymer determines.

The dosage of the monomers such as conjugated diene compound has and number related to the degree of polymerization relative to the dosage of polymerization initiator Average molecular weight and/or the relevant tendency of weight average molecular weight.It therefore, can be in order to increase the molecular weight of conjugated diene polymer It is adjusted to the direction for reducing polymerization initiator；In order to reduce molecular weight, can be adjusted to the direction for increasing polymerization initiator amount.

Organo monolithium compounds as polymerization initiator are preferably the alkyl lithium compounds or two with substituted-amino Alkyl amino lithium.In the case where using these compounds, can be obtained has the nitrogen-atoms for constituting amino in polymerization initiating terminal Conjugated diene polymer.

Substituted-amino is the amino of structure without reactive hydrogen or being protected to reactive hydrogen.

As the alkyl lithium compounds with the amino without reactive hydrogen, it can enumerate but be not limited to such as 3- dimethylamino Base propyl lithium, 3- diethyl amino propyl lithium, 4- (methylpropylamino) butyl lithium, 4- hexamethyleneimino butyl lithium.

As the alkyl lithium compounds of the amino with the structure protected to reactive hydrogen, it can enumerate but be not limited to Such as the bis- trimethylsilylaminopropyl lithiums of 3-, 4- trimethylsilyl methyl aminobutyl lithium.

As lithium dialkyl amides, it can enumerate but be not limited to such as dimethylamino lithium, diethylamino lithium, dipropyl Lithium amide, dibutylamino lithium, di-n-hexyl lithium amide, diheptyl lithium amide, lithium diisopropylamine, dioctylamino lithium, Two -2- ethylhexylamino lithiums, didecylamino lithium, ethylpropylamino lithium, ethyl-butyl lithium amide, Ethylbenzyl amino Lithium, methylphenethyl lithium amide, hexamethyleneimino lithium, pyrrolidinyl lithium, piperidyl lithium, heptamethylene imino group lithium, Quinoline base lithium, 1- lithium Azacyclooctane, 6- lithium -1,3,3- trimethyl -6- azabicyclo [3.2.1] octane, 1- lithium -1,2,3,6- four Pyridinium hydroxide.

These organo monolithium compounds with substituted-amino can also with polymerizable monomer, such as 1,3- butadiene, The monomers such as isoprene, styrene marginally react, come in the form of the organo monolithium compounds of solubilized oligomer using.

Organo monolithium compounds are preferably alkyl lithium compounds.It can be obtained in the case where using the compound and originated in polymerization End has the conjugated diene polymer of alkyl.

As alkyl lithium compounds, can enumerate but be not limited to for example n-BuLi, s-butyl lithium, tert-butyl lithium, just oneself Base lithium, benzyl lithium, phenyl lithium, stilbene lithium.

As alkyl lithium compounds, from the easiness aspect of easiness and polymerization reactor control that industry obtains, It is preferred that n-BuLi, s-butyl lithium.

One kind can be only used alone in these organo monolithium compounds, can also share two or more.

In addition, organo monolithium compounds can be shared with other organo-metallic compounds.

As the organo-metallic compound, it can enumerate but be not limited to such as alkaline earth metal compound, otheralkali metal Close object, other organo-metallic compounds.

As alkaline earth metal compound, it can enumerate but be not limited to such as organo-magnesium compound, organocalcium compound, organic Strontium compound.In addition it can enumerate alkoxide, sulfonate, carbonate, the amide compound of alkaline-earth metal.As organic-magnesium chemical combination Object can be enumerated but be not limited to such as dibutylmagnesium, ethyl-butyl magnesium.

As other organo-metallic compounds, it can be cited for example that organo-aluminum compound.

In polymerization process, as polymerization reaction form, can enumerate but be not limited to it is for example intermittent (also referred to as " in batches Formula "), continuous polymerization reaction form.

In continous way, 1 or 2 or more the reactor through linking can be used.Continuous reactor for example makes With the groove profile with blender, the reactor of cast.It is preferably that monomer, atent solvent and polymerization initiator is continuous in continous way It is loaded into reactor, the polymer solution comprising polymer is obtained in the reactor, polymer solution is continuously discharged.

Intermittent reactor is for example using the tank reactor with blender.In intermittent, monomer, inertia are preferably inserted Solvent and polymerization initiator continuously or discontinuously add monomer in polymerization as needed, are included in the reactor The polymer solution of polymer, is discharged polymer solution after polymerization.

In the polymerization process of the manufacturing method of the modified conjugated diene polymer of present embodiment, in order to at high proportion The conjugated diene polymer of active end is obtained, preferably polymer can continuously be discharged, in a short time for next Walk the continuous polymerization reaction form of reaction.

Polymerization process is preferably polymerize in atent solvent.

As atent solvent, it can be cited for example that the hydrocarbon system solvents such as saturated hydrocarbons, aromatic hydrocarbon.

As hydrocarbon system solvent, it can enumerate but be not limited to the aliphatic hydrocarbon such as butane, pentane, hexane, heptane；Ring penta The clicyclic hydrocarbons such as alkane, hexamethylene, methyl cyclopentane, hexahydrotoluene；Aromatic hydrocarbons such as benzene,toluene,xylene and by these Mixture constitute hydrocarbon.

Before for polymerization reaction, by as the allene class of impurity and acetylene class using organo-metallic compound into Row processing, thus tends to obtain the conjugated diene polymer of the reactive terminal with high concentration, it is intended to obtain high modification The modified conjugated diene polymer of rate, thus be preferred.

Polar compound can be added in polymerization process.Thus aromatic ethenyl compound and conjugation can be made by having Diolefin compound random copolymerization, can also come as the vinyl agent of the micro-structure for controlling conjugated diene portion using Tendency.In addition with polymerization reaction in terms of also with effect tendency.

As polar compound, it can enumerate but be not limited to such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol two Bis- (the 2- tetrahydrofurans of methyl ether, butyl cellosolve, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, dimethoxy benzene, 2,2- Base) ethers such as propane；The tertiary amines chemical combination such as tetramethylethylenediamine, two piperidino ethane, trimethylamine, triethylamine, pyridine, quinuclidine Object；The alkali metal alcohols salt compounds such as tert-pentyl alcohol potassium, potassium tert-butoxide, sodium tert-butoxide, amylalcohol sodium；Phosphine compounds such as triphenylphosphine etc..

One kind can be only used alone in these polar compounds, can also share two or more.

The dosage of polar compound is not particularly limited, can be selected according to purpose etc., is caused relative to 1 mole of polymerized Agent, preferably 0.01 mole or more 100 moles or less.Tune of the polar compound as the micro-structure of polymer conjugated diene portion Section agent is used as vinyl agent as expected vinyl bonds resultants can appropriately use.

Many polar compounds have in the copolymerization of conjugated diene compound and aromatic ethenyl compound simultaneously The randomization effect of effect has the adjustment of the distribution regulator or styrene block amount that can be used as aromatic ethenyl compound The tendency of agent.

As the method for making conjugated diene compound Yu aromatic ethenyl compound randomization, can be used for example Japanese It is anti-to cause copolymerization for the documented total amount using styrene and a part of 1,3- butadiene in tekiaki 59-140211 bulletin The method answered, discontinuously add remaining 1,3- butadiene in the way of copolyreaction.

What the conjugated diene polymer before aftermentioned modified-reaction process obtained in polymerization process was preferably measured at 110 DEG C Mooney viscosity be 10 or more 90 hereinafter, more preferably 15 or more 85 or less, be still more preferably 20 or more 60 or less.

When the Mooney viscosity of conjugated diene polymer is above range, the modified conjugated diene polymerization of present embodiment Object has the tendency of processability and excellent wear resistance.

To the bonding conjugated diene in the conjugated diene polymer or modified conjugated diene polymer of present embodiment Amount is not particularly limited, preferably 40 mass % or more, 100 mass % or less, more preferably 55 mass % or more, 80 mass % with Under.

In addition, to the bonding fragrance in the conjugated diene polymer or modified conjugated diene polymer of present embodiment Race's ethylene base unit weight is not particularly limited, preferably 0 mass % or more, 60 mass % or less, more preferably 20 mass % or more, 45 matter Measure % or less.

When bonding conjugated diene amount and bonding aromatic vinyl base unit weight are above range, have and the low magnetic after sulfide is made The balance and destruction characteristic and the more excellent tendency of abrasion performance of stagnant lossy and anti-slippery.

Herein, the ultraviolet light absorption that bonding aromatic vinyl base unit weight can use phenyl is measured, and thus can also be found out It is bonded conjugated diene amount.Specifically, can be measured according to the method recorded in aftermentioned embodiment.

In the conjugated diene polymer or modified conjugated diene polymer of present embodiment, conjugated diene is bonded Vinyl bonds resultant in unit is not particularly limited, and 75 moles of % or less of preferably 10 moles of % or more, more preferably 20 rubs You are 65 moles of % or less of % or more.

When vinyl bonds resultant is above range, there is the flat of after sulfide is made low magnetic hystersis loss and anti-slippery Weighing apparatus and abrasion performance and breakdown strength more excellent tendency.

Herein, in the case where modified conjugated diene polymer is the copolymer of butadiene and styrene, can pass through Hampton method (R.R.Hampton, Analytical Chemistry, 21,923 (1949)) finds out butadiene bonding units In vinyl bonds resultant (1,2- bonded amount).Specifically, can be measured by the method recorded in aftermentioned embodiment.

About the micro-structure of modified conjugated diene polymer, in the modified conjugated diene polymer of present embodiment Each bonded amount be in the glass transition temperature of above-mentioned numberical range and modified conjugated diene polymer and be in -50 DEG C When range more than and less than -20 DEG C, low magnetic hystersis loss can be obtained and the balance of anti-slippery is further excellent by having Sulfide tendency.

It is recorded while with the heating of defined temperature range about glass transition temperature according to ISO22768:2006 DSC curve regard the summit (inflection point) of DSC differential curve as glass transition temperature.Specifically, aftermentioned implementation can be passed through The method recorded in example is measured.

The case where modified conjugated diene polymer of present embodiment is conjugated diene-aromatic vinyl copolymer Under, block number made of preferably 30 or more aromatic vinyl units links is few or is not present.More specifically, in copolymer In the case where for butadiene-styrene copolymer, using Kolthoff method (I.M.KOLTHOFF, et al., The method recorded in J.Polym.Sci.1,429 (1946)) by copolymer decompose and to the polystyrene amount insoluble in methanol into In the known method of row analysis, block made of 30 or more aromatic vinyl units links is excellent relative to the total amount of copolymer It is selected as 5.0 mass % or less, more preferably 3.0 mass % or less.

(modified-reaction process)

In modified-reaction process, the conjugated diene polymer for obtaining benefit with the aforedescribed process is reacted with modifying agent, should Connection group that modifying agent is reacted with the reactive terminal with the conjugated diene polymer and then have with filler has close With the particular functional group of property or bonding reaction.

In this case, particular functional group possessed by modifying agent can also have both the effect as connection group.In addition, It is preferred that implementing modified-reaction process immediately after polymerization process.In this case, have and the high modified conjugation of degree of modification can be obtained The tendency of diene polymer.

As modifying agent, the end of straight-chain can be obtained when the use of connection group being the compound of simple function or 2 functions Modified diene based polymer；When the use of connection group being the polyfunctional compound of 3 functions or more, the modification of branched can be obtained Diene polymer.

As modifying agent, it is preferable to use the simple function comprising at least one of nitrogen, silicon, tin, phosphorus, oxygen, sulphur, halogen element Or polyfunctional compound.In addition, reacted by being added terminal-modified dose comprising generating agent, it can be by structure It is directed into above-mentioned modified conjugated diene polymer.It additionally can be used in the molecule containing a plurality of comprising these elements Functional group modifying agent or modifying agent containing the functional group comprising these a plurality of elements.

As modifying agent used in modified-reaction process, preferably there is hydroxyl, carboxyl, primary amino group or secondary amino group isoreactivity Hydrogen is few or the compound of functional group without reactive hydrogen.Reactive hydrogen, which has, inactivates the reactive terminal of conjugated diene polymer Tendency.

<the specific record of modifying agent>

As nitrogenous compound, it can enumerate but be not limited to such as isocyanate compound, isothiocyanate compound, different Cyanurate derivative, the carbonyls of nitrogenous base, the vinyl compound of nitrogenous base, epoxide of nitrogenous base etc..

As silicon-containing compound, it can enumerate but be not limited to such as halogenated silicon compound, epoxidation silicon compound, vinyl SiClx compound, alkoxy-silicon compound, alkoxy-silicon compound containing nitrogen base etc..

As sn-containing compound, it can enumerate but be not limited to such as halogenation tin compound, organotin carboxylate's ester compounds.

As phosphorus-containing compound, it can enumerate but be not limited to such as bi-ester of phosphite, phosphino- compound.

As oxygenatedchemicals, it can enumerate but be not limited to such as epoxide, ether compound, ester compounds.

As sulfur-containing compound, it can enumerate but be not limited to such as mercapto derivatives, thiocarbonyl compound, isothiocyanic acid Ester etc..

As halogen contained compound, above-mentioned halogenated silicon compound, halogenation tin compound etc. can be enumerated but are not limited to.

As generating agent, it can enumerate but be not limited to for example form the protection amine compounds (life of primary amine or secondary amine At ammonium), protection phosphine compound (generate phosphorus) that hydrogenation phosphine can be formed, hydroxyl can be formed, the compound of mercaptan (generates oxygen , sulphur) etc., it is preferable to use being respectively provided with generating agent in the molecule and for being bonded above-mentioned modified conjugated diene polymer Terminal-modified dose of functional group.

As the above-mentioned functional group for β-cyclodextrin conjugated diene polymer, carbonyl (ketone, ester etc.), second can be enumerated The unsaturated groups such as alkenyl, epoxy group, silyl halide, alkoxysilyl group etc..

Modifying agent preferably as nitrogenous compound the compound with nitrogen-containing functional group, as this with nitrogen-containing functional group Compound, preferably do not have reactive hydrogen amine compounds, for example, tertiary amine compound, above-mentioned reactive hydrogen are by protecting group Instead of protectionization amine compounds, group with imine moiety represented by general formula-N=C.

As the isocyanate compound for the nitrogenous compound for belonging to modifying agent, it can enumerate but be not limited to such as 2,4- benzyl Support diisocyanate, 2,6- benzyl supports diisocyanate, two isocyanide of diphenyl methane of methyl diphenylene diisocyanate, aggretion type Acid esters (C-MDI), phenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, butyl isocyanate, 1,3, 5- benzene triisocyanate etc..

As isothiocyanate compound, it can enumerate but be not limited to such as 2,4- benzyl support diisothio-cyanate, 2,6- benzyl Support diisothio-cyanate, diphenyl methane diisothio-cyanate, aggretion type diphenyl methane diisothio-cyanate (C-MDI), Phenyl isothiocyanate, isophorone diisothio-cyanate, hexa-methylene diisothio-cyanate, butyl isothiocyanate, 1,3,5- benzene Three isothiocyanates etc..

As isocyanuric acid derivative, it can enumerate but be not limited to such as 1,3,5- tri- (3- trimethoxysilyls third Base) isocyanuric acid ester, 1,3,5- tri- (3- triethoxysilylpropyltetrasulfide) isocyanuric acid ester, the (ethylene oxide -2- of 1,3,5- tri- Base) -1,3,5- triazine -2,4,6- triketone, 1,3,5- tri- (isocyanatomethyl) -1,3,5- triazine -2,4,6- triketone, 1,3, 5- trivinyl -1,3,5- triazine -2,4,6- triketone etc..

As the carbonyls of nitrogenous base, it can enumerate but be not limited to such as 1,3-Dimethyl-2-imidazolidinone, 1- first Base -3- ethyl -2- imidazolone, 1- methyl -3- (2- methoxy ethyl) -2- imidazolone, n-methyl-2-pyrrolidone, N- Methyl -2- piperidones, N- methyl -2- quinolone, 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (dimethylamino) two Benzophenone, methyl-2-pyridyl ketone, methyl -4- pyridyl ketone, propyl -2- pyridyl ketone, two -4- pyridyl ketones, 2- benzoyl Yl pyridines, N, N, N ', N '-tetramethylurea, N, N- dimethyl-N ', N '-diphenyl urea, N, N- diethylamino formic acid methyl esters, N, N- diethyl acetamide, N, N- dimethyl-N ', N '-dimethylaminoacetyl amine, N, N- lutidines formamide, N, N- diformazan Base Pyrazinamide etc..

As the vinyl compound of nitrogenous base, it can enumerate but be not limited to such as N,N-DMAA, N, N- Dimethylmethacryl amide, N- methylmaleimido, N-Methyl-o-phthalimide, N, the bis- trimethyl silyls of N- Acrylamide, morpholinyl acrylamide, 3- (2- dimethylamino ethyl) styrene, (dimethylamino) dimethyl -4- vinyl benzene Base silane, 4,4 '-ethenylidenes bis- (N, accelerines), 4,4 '-ethenylidenes bis- (N, N- diethylanilines), 1,1- are bis- (4- morpholino phenyl) ethylene, 1- phenyl -1- (4-N, TMSDMA N dimethylamine base phenyl) ethylene etc..

As the epoxide of nitrogenous base, it can be cited for example that containing the hydrocarbon compound with the epoxy group of amino bonded, The substance with the epoxy group being bonded with ether can also be enumerated, but is not limited to these.

As the epoxide of the nitrogenous base, for example, compound represented by general formula (1).

[changing 6]

In above-mentioned formula (1), R is for alkyl more than divalent or with oxygen, thioether, thio ketone selected from ether, epoxy, ketone etc. Deng at least one of the nitrogen of sulphur, tertiary amino, imino group etc. polar group divalent more than organic group.

It can be straight-chain, branched, cricoid alkyl, including alkylene that alkyl more than divalent, which is saturated or unsaturated, Base, alkenylene, phenylene etc..Preferably carbon atom number be 1~20 alkyl.Concrete example is it can be cited for example that methylene, sub- second Bis- (the methylene)-hexamethylenes of base, butylidene, cyclohexylidene, 1,3-, bis- (the ethylidene)-hexamethylenes of 1,3-, adjacent phenylene, Asia Phenyl, to phenylene, meta-xylene, paraxylene, bis- (phenylene)-methane etc..

In above-mentioned formula (1), R¹、R⁴It is the alkyl that carbon atom number is 1~10, R¹、R⁴It mutually can be different.R²、R⁵Be hydrogen or The alkyl that carbon atom number is 1~10, R²、R⁵It mutually can be different.

R³For the structure of alkyl or following formula (2) that carbon atom number is 1~10.

R¹、R²、R³It can be mutually bonded and become cyclic structure.

In addition, R³In the case where for alkyl, it can be mutually bonded with R and become cyclic structure, in this case, R³It can be with For singly-bound.

[changing 7]

In above-mentioned formula (2), R¹、R²With the R of above-mentioned formula (1)¹、R²It similarly defines, R¹、R²It mutually can be different.

As the epoxide for the nitrogenous base for being used as modifying agent, preferably with the chemical combination of the alkyl containing epoxy group Object, more preferably with the compound of the alkyl containing glycidyl.

As the alkyl containing the epoxy group being bonded with amino or ether, for example, glycidyl-amino, two Glycidyl-amino or glycidoxy.Further preferred molecular structure is to be respectively provided with glycidyl-amino or two contractings The compound containing epoxy group of water glyceryl amino and glycidoxy, as represented by the following general formula (3).

[changing 8]

In above-mentioned formula (3), R is defined in the same manner as the R of above-mentioned formula (1), R⁶It is the alkyl or following formula that carbon atom number is 1~10 (4) structure.

R⁶In the case where for alkyl, it can be mutually bonded with R and become cyclic structure, in this case, R⁶It can be single Key.

In formula (3), the integer that n is 1 or more, the integer that m is 0 or 1 or more.

[changing 9]

As the epoxide for the nitrogenous base for being used as modifying agent, more preferably in the molecule with 1 or more two contractings The compound of the glycidoxy of water glyceryl amino and 1 or more.

As the epoxide for the nitrogenous base for being used as modifying agent, such as N can be enumerated but be not limited to, N- bis- shrinks sweet Oil base -4- glycidoxy aniline, 1-N, N- diglycidyl amino methyl -4- glycidoxy-hexamethylene, 4- (4- ring Oxygen propoxyphenyl)-(N, N- diglycidyl) aniline, 4- (4- glycidoxy phenoxy group)-(N, N- 2-glycidyl Base) aniline, 4- (4- glycidoxy benzyl)-(N, N- diglycidyl) aniline, 4- (N, N '-diglycidyl -2- piperazine Piperazine base)-glycidoxy benzene, 1,3- bis- (N, N- diglycidyl amino methyl) hexamethylenes, N, N, N ', N '-four shrinks sweet Oil base m-xylene diamine, 4,4- methylene-bis- (N, N- diglycidylaniline), bis- (N, the N- diglycidyls of 1,4- Amino) hexamethylene, N, N, N ', N '-four glycidyl group p-phenylenediamine, 4,4 '-bis- (diglycidyl amino) benzophenone, 4- (4- glycidyl piperazinyl)-(N, N- diglycidyl) aniline, 2- [2- (N, N- diglycidyl amino) second Base] -1- glycidyl pyrrolidines, N, N- diglycidylaniline, 4,4 '-diglycidyls-dibenzylmethyl amine, N, N- diglycidylaniline, N, N- diglycidyl ortho-aminotoluene, N, N- diglycidyl aminomethyl cyclohexane etc..

Among these, N can be enumerated, N- diglycidyl -4- glycidoxy aniline, 1,3- are bis-, and (N, N- bis- shrinks Glyceryl amino methyl) hexamethylene is as preferred compound.

As the halogenated silicon compound for belonging to modifying agent, it can enumerate but be not limited to such as dibutyldichlorosilane, methyl Trichlorosilane, dimethyldichlorosilane, dimethyl dichlorosilane (DMCS), trim,ethylchlorosilane, tetrachloro silicane, three (trimethyl silyl oxygen Base) chlorosilane, three (dimethylamino) chlorosilanes, disilicone hexachloride, bis- (silicochloroform base) methane, bis- (the three chloromethane silicon of 1,2- Alkyl) ethane, bis- (methyl dichloro silicyl) ethane of 1,2-, bis- (silicochloroform base) butane of 1,4-, 1,4 bis- (methyl two Chlorosilyl) butane etc..

As the epoxidation silicon compound for belonging to modifying agent, it can enumerate but be not limited to such as 3- glycidoxypropyl group three Methoxy silane, 3- epoxy propoxy propyl triethoxysilane, 3- glycidoxypropyl diethoxy silane, epoxy Modified silicone etc..

As the alkoxy-silicon compound for belonging to modifying agent, it can enumerate but be not limited to such as tetramethoxy-silicane, tetrem Oxysilane, triple phenoxyl methyl-monosilane, methoxy substitution polysiloxane etc..

As the alkoxy-silicon compound for the nitrogenous base for belonging to modifying agent, it can enumerate but be not limited to such as 3- dimethylamino Propyl trimethoxy silicane, 3- dimethylamino-propyl methyl dimethoxysilane, 3- diethyl amino propyl triethoxysilane, Morpholinyl propyl trimethoxy silicane, 3- piperidino propyl-triethoxysilicane, 3- hexamethyleneimino hydroxypropyl methyl Diethoxy silane, 3- (4- methyl-1-piperazinyl) propyl-triethoxysilicane, 1- [3- (triethoxysilyl)-the third Base] -3- methylhexa-hydro pyrimidine, 3- (4- trimethyl silyl -1- piperazinyl) propyl-triethoxysilicane, 3- (tri- second of 3- Base silicyl -1- imidazolidinyl) hydroxypropyl methyl diethoxy silane, 3- (3- trimethyl silyl -1- hexahydro-pyrimidine Base) propyl trimethoxy silicane, 3- dimethylamino -2- (dimethylamino methyl) propyl trimethoxy silicane, bis- (3- dimethoxys Methyl silicane base propyl)-N- methyl amine, bis- (3- trimethoxy-silylpropyl)-N- methyl amines, bis- (3- triethoxies Silylpropyl) methyl amine, three (trimethoxysilyl) amine, three (3- trimethoxy-silylpropyl) amine, N, N, N ', N '-four (3- trimethoxy-silylpropyl) ethylenediamine, 3- isocyanatopropyl trimethoxy silane, 3- cyano third Base trimethoxy silane, 2,2- dimethoxy -1- (3- trimethoxy-silylpropyl) -1- azepine -2- silacyclopentan, 2, 2- diethoxy -1- (3- triethoxysilylpropyltetrasulfide) -1- azepine -2- silacyclopentan, 2,2- dimethoxy -1- (4- Trimethoxysilyl butyl) -1- azepine -2- Silinane, 2,2- dimethoxy -1- (3- dimethoxy-methyl first silicon Alkyl propyl) -1- azepine -2- silacyclopentan, 2,2- dimethoxy -1- phenyl -1- azepine -2- silacyclopentan, 2,2- bis- Ethyoxyl-1- butyl-1- azepine-2- silacyclopentan, 2,2- dimethoxy-1- methyl-1-azepine-2- silacyclopentan, 2, 2- dimethoxy -8- (4- methyl piperazine base) methyl-1,6- dioxa -2- sila cyclooctane, 2,2- dimethoxy -8- (N, N- Diethylamino) methyl-1,6- dioxa -2- sila cyclooctane etc..

About the protection amine compounds for forming primary amine or secondary amine for belonging to modifying agent, as in the molecule with insatiable hunger With the compound of key and protectionization amine, it can enumerate but be not limited to such as 4, bis- [bis- (the trimethyl first silicon of N, N- of 4 '-ethenylidenes Alkyl) aniline], bis- [N, N- are bis- for 4,4 '-ethenylidenes bis- [bis- (triethylsilyl) aniline of N, N-], 4,4 '-ethenylidenes (t-butyldimethylsilyl) aniline], 4,4 '-ethenylidenes bis- [N- methyl-N- (trimethyl silyl) aniline], 4, 4 '-ethenylidenes bis- [N- ethyl-N- (trimethyl silyl) aniline], the bis- [N- methyl-N- (triethyl groups of 4,4 '-ethenylidenes Silicyl) aniline], 4,4 '-ethenylidenes bis- [N- ethyl-N- (triethylsilyl) aniline], 4,4 '-ethenylidenes it is double [N- methyl-N- (t-butyldimethylsilyl) aniline], bis- [N- ethyl-N- (fert-butyidimethylsilyls of 4,4 '-ethenylidenes Silicyl) aniline], 1- [bis- (trimethyl silyl) aminophenyls of 4-N, N-] -1- [4-N- methyl-N- (trimethyl first silicon Alkyl) aminophenyl] ethylene, 1- [bis- (trimethyl silyl) aminophenyls of 4-N, N-] -1- [4-N, N- Dimethylaminobenzene Base] ethylene etc..

About the protection amine compounds for forming primary amine or secondary amine for belonging to modifying agent, as in the molecule with alcoxyl Such as N, bis- (trimethyl silyl) aminopropyls three of N- can be enumerated but be not limited to the compound of base silane and protectionization amine Methoxy silane, N, bis- (trimethyl silyl) aminopropylmethyldimethoxysilanes of N-, N, the bis- (trimethyl silyls of N- Base) aminopropyltriethoxywerene werene, N, bis- (trimethyl silyl) the amino propyl methyl diethoxy silanes of N-, N, N- is bis- (trimethyl silyl) amino-ethyl trimethoxy silane, N, bis- (trimethyl silyl) the aminoethyl methyl diethoxies of N- Base silane, N, bis- (triethylsilyl) the amino propyl methyl diethoxy silanes of N-, 3- (4- trimethyl silyl -1- Piperazinyl) propyl-triethoxysilicane, 3- (3- triethylsilyl -1- imidazolidinyl) hydroxypropyl methyl diethoxy silane, 3- (3- trimethyl silyl -1- hexahydro-pyrimidine base) propyl trimethoxy silicane, 2,2- dimethoxy -1- (3- trimethoxy Base silylpropyl) -1- azepine -2- silacyclopentan, 2,2- diethoxy -1- (3- triethoxysilylpropyltetrasulfide) - 1- azepine -2- silacyclopentan, 2,2- dimethoxy -1- (4- trimethoxysilyl butyl) -1- azepine -2- sila hexamethylene Alkane, 2,2- dimethoxy -1- (3- dimethoxymethylsilylpropyl) -1- azepine -2- silacyclopentan, 2,2- dimethoxy Base -1- phenyl -1- azepine -2- silacyclopentan, 2,2- diethoxy -1- butyl -1- azepine -2- silacyclopentan, 2,2- bis- Methoxyl group-1- methyl-1-azepine-2- silacyclopentan etc..

As the halogenation tin compound for belonging to modifying agent, tin tetrachloride, tin tetrabromide, butyl three can be enumerated but are not limited to Stannic chloride, octyl tin trichloride, dimethyl tin bibromide, dibutyl tin dichloride, tributyltin chloride, trioctylphosphine stannic chloride, Bis- (trichlorine stannyl) ethane of triphenyl tin chloride, 1,2-, bis- (methyl dichloro stannyl) ethane of 1,2-, 1,4- bis- (three Chlorine stannyl) butane, 1,4 bis- (methyl dichloro stannyl) butane etc..

As the organotin carboxylate's ester compounds for belonging to modifying agent, it can enumerate but be not limited to such as three stearic acid of ethyl tin Double caprylates of ester, three caprylate of butyl tin, butyl tin tristearate, butyl tin trilaurin, dibutyl tin etc..

As the bi-ester of phosphite for belonging to modifying agent, it can enumerate but be not limited to such as Trimethyl phosphite, phosphorous Sour tributyl, phosphorous acid triple phenoxyl ester etc..

As the phosphino- compound for belonging to modifying agent, such as P, P- bis- (trimethyl silyls) can be enumerated but are not limited to Phosphino- propyl trimethoxy silicane, P, the protections phosphino- such as bis- (triethylsilyl) phosphino- hydroxypropyl methyl Ethoxysilanes of P- Compound；3- dimethyl phosphino- propyl trimethoxy silicane, 3- diphenylphosphino propyl trimethoxy silicane etc..

As the oxygenatedchemicals for belonging to modifying agent, it can enumerate but be not limited to such as ethylene glycol diglycidylether, sweet The polyglycidyl ethers such as oily triglycidyl ether；1,4- diglycidyl benzene, 1,3,5- triglycidyl group benzene, polycyclic oxidation The polyepoxides such as liquid polybutadiene, epoxidised soybean oil, epoxidised linseed oil；Dimethyl adipate, adipic acid two The ester compounds such as ethyl ester, dimethyl terephthalate (DMT), diethyl terephthalate, they generate hydroxyl in polymer ends.

As the sulfur-containing compound for belonging to modifying agent, it can enumerate but be not limited to such as S- trimethyl silyl thio third The protections mercaptan compounds, S- first such as base trimethoxy silane, S- triethylsilyl sulfopropyl methyl diethylsilane Mercaptopropyl trimethoxy silane, S- ethylsuleenyl propyl methyldiethoxysilane, N, N- diethyldithiocar bamic acid second Ester, phenyl isothiocyanate, 1,4- diisothiocyanic acid phenyl ester, hexa-methylene diisothio-cyanate, butyl isothiocyanate etc..

As modifying agent, it is however preferred to have the compound of siliceous functional group, as the siliceous functional group, it can be cited for example that Alkoxysilyl or silanol group.

Above-mentioned alkoxysilyl have for example react with reactive terminal possessed by conjugated diene polymer, End and the tendency of the silicon of modifying residues being bonded for dissociateing alkoxy lithium, forming conjugated diene polymer chain.By 1 point The sum of SiOR possessed by sub- modifying agent is subtracted by reaction and value obtained from the SiOR number of reduction is modifying residues institute The number for the alkoxysilyl having.In addition, aza-silicon ring group possessed by modifying agent formed > N-Li bonding and conjugation two Alkene based polymer end is bonded with the silicon of modifying residues.It should be noted that > N-Li bonding has when being finished The effect of water etc. and easily become the > tendency of NH and LiOH.In addition, in modifying agent, unreacted and remaining alkoxy first Silylation has the function of water when can be finished etc. and easily becomes the tendency of silanol (Si-OH yl).

In modified-reaction process, make the feelings that relative to 1 silicon atom there is the compound of 3 alkoxies to react Under condition, the reactive terminal of 3 moles of conjugated diene polymer is made to react relative to 1 mole of trialkoxysilane base In the case where, have react at most 2 moles of conjugated diene polymer, 1 mole of alkoxy unreacted and remain Tendency.This point is not reacted by 1 mole of conjugated diene polymer and residual in the form of unreacted polymer It stays and is confirmed.It should be noted that by sending out alkoxy more with the reactive terminal of conjugated diene polymer When being able to suppress finishing, when storage condensation reaction occurs for raw reaction, has be able to suppress that polymer viscosity substantially changes to incline To.It is preferable to use the modifying agent relative to 1 silicon atom with 1 alkoxy.

Reaction temperature in modified-reaction process is preferably same temperature with the polymerization temperature of conjugated diene polymer, Particularly preferably after polymerisation without the temperature of heating.In particular, it is preferred that for 0 DEG C or more 120 DEG C or less, more preferably 50 DEG C or more 100 DEG C or less.

Reaction time in modified-reaction process is preferably 10 seconds or more, more preferably 30 seconds or more.

Mixing in modified-reaction process can be mechanical stirring, utilize any one of stirring of static mixer etc.. Polymerization process is in continuous situation, and modified-reaction process is preferably also continous way.

Reactor in modified-reaction process is for example using the groove profile with blender, the reactor of cast.Modifying agent can be with It is continuously fed into reactor after being diluted using atent solvent.In the case that polymerization process is intermittent, it can use to polymerization The method that modifying agent is put into reactor, is modified reaction process alternatively, it is also possible to be transported in another reactor.

As the modifying agent of the modified conjugated diene polymer for manufacturing present embodiment, the following general formula can be enumerated (VI) compound represented is as preferred compound.

[changing 10]

In formula (VI), R¹²~R¹⁴Singly-bound or carbon atom number are each independently represented as 1~20 alkylidene, R¹⁵~R¹⁸With R²⁰Each independently represent the alkyl that carbon atom number is 1~20, R¹⁹And R²²Each independently representing carbon atom number is 1~20 Alkylidene, R²¹Indicate that carbon atom number is 1~20 alkyl or trialkylsilkl.

M indicates that 1~3 integer, p indicate 1 or 2.

There are the R in the case where a plurality of¹²~R²², m and p it is respectively independent.

I indicate 0~6 integer, j indicate 0~6 integer, k indicate 0~6 integer, (i+j+k) indicate 1~10 it is whole Number.

A indicate singly-bound, carbon atom number be 1~20 alkyl or have select free oxygen atom, nitrogen-atoms, silicon atom, sulphur At least one of the group of atom, phosphorus atoms composition atom and the organic group for not having reactive hydrogen.

As alkyl represented by A, include saturation, unsaturated, aliphatic and aromatic alkyl.Without reactive hydrogen Organic group be will not make reactive terminal possessed by conjugated diene polymer inactivate organic group.As the organic group Group, for without hydroxyl (- OH), secondary amino group (> NH), primary amino group (- NH₂), the functional group of the active hydrogen such as sulfydryl (- SH) Organic group.It should be noted that can also not have A in the case that (i+j+k) is 1.

In above-mentioned formula (VI), A preferably indicates any one of the following general formula (II)~(V).

[changing 11]

In above-mentioned formula (II), B¹The alkyl that expression singly-bound or carbon atom number are 1~20, a indicate 1~10 integer, exist B in the case where a plurality of¹It is respectively independent.

[changing 12]

In above-mentioned formula (III), B²The alkyl that expression singly-bound or carbon atom number are 1~20, B³Indicate that carbon atom number is 1~20 Alkyl, a indicate 1~10 integer, be respectively present it is a plurality of in the case where B²And B³It is respectively independent.

[changing 13]

In above-mentioned formula (IV), B⁴The alkyl that expression singly-bound or carbon atom number are 1~20, a indicate 1~10 integer, exist B in the case where a plurality of⁴It is respectively independent.

[changing 14]

In above-mentioned formula (V), B⁵The alkyl that expression singly-bound or carbon atom number are 1~20, a indicate 1~10 integer, exist multiple B in the case where several⁵It is respectively independent.

By making any one of the above-mentioned formula of A (II)~(V) in above-mentioned formula (VI), it is total that following modifications can be obtained Yoke diene polymer, the polymer is low with the adhesion of metal surface when can be obtained when processing and vulcanizing, sulfide is made Afterwards with the rubber composition for tire of high abrasion resistance.

About the modifying agent of above-mentioned formula (VI), the modifying agent for being 1~2 as (i+j+k) (also includes and above-mentioned modifying agent Duplicate substance) it can enumerate but be not limited to such as 3- dimethoxymethylsilylpropyl dimethylamine (1 function), 3- front three Oxygroup silylpropyl dimethylamine (2 function), bis- (3- trimethoxy-silylpropyl) methyl amines (4 function), bis- (3- bis- Methoxy silylpropyl) methyl amine (2 function), (3- trimethoxy-silylpropyl)-[3- (2,2- dimethoxy Base -1- azepine -2- silacyclopentan) propyl] ethamine (4 function), [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) Propyl]-(3- trimethoxy-silylpropyl) methyl amine (4 function), bis- [3- (2,2- dimethoxy -1- azepine -2- silas Pentamethylene) propyl] methyl amine (4 function), bis- (3- triethoxysilylpropyltetrasulfide) ethamine (4 function), 1- (3- triethoxy Silylpropyl) -2,2- diethoxy -1- azepine -2- silacyclopentan (4 function), 1- (3- dimethoxy-methyl monosilane Base propyl) -2,2- dimethoxy -1- azepine -2- silacyclopentan (3 function), [3- (2,2- diethoxy -1- azepine -2- silicon Heterocycle pentane) propyl]-(3- diethoxy ethyl silicane base propyl) methyl amine (3 function), bis- [3- (2,2- diethoxies- 1- azepine -2- silacyclopentan) propyl] methyl amine (4 function), (3- trimethoxy-silylpropyl)-[3- (1- methoxyl group - 2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl]-methyl amine (3 function).

When modifying agent is polyfunctional compound and (i+j+k) is 3 or more, as the A in above-mentioned formula (VI) by above-mentioned formula (II) such as three (3- trimethoxy-silylpropyl) amine, double can be enumerated but be not limited to the modifying agent in the case where indicating (3- trimethoxy-silylpropyl)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] amine, bis- [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl]-(3- trimethoxy-silylpropyl) amine, three [3- (2,2- Dimethoxy -1- azepine -2- silacyclopentan) propyl] amine, three (3- triethoxysilyl propyl) amine, bis- (3- triethoxies Silylpropyl)-[3- (2,2- diethoxy -1- azepine -2- silacyclopentan) propyl] amine, bis- [3- (2,2- diethoxies Base -1- azepine -2- silacyclopentan) propyl]-(3- triethoxysilylpropyltetrasulfide) amine, three [3- (2,2- diethoxy -1- Azepine -2- silacyclopentan) propyl] amine, four (3- trimethoxy-silylpropyl) -1,3- propane diamine, three (3- trimethoxies Silylpropyl)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- propane diamine, bis- (3- front threes Oxygroup silylpropyl)-bis- [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- propane diamine, three [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl]-(3- trimethoxy-silylpropyl) -1,3- the third two Amine, four [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- propane diamine, three (3- trimethoxy first silicon Alkyl propyl)-[3- (1- methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- propane diamine, Bis- (3- trimethoxy-silylpropyls)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl]-[3- (1- Methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- propane diamine, bis- [3- (2,2- dimethoxies Base -1- azepine -2- silacyclopentan) propyl]-(3- trimethoxy-silylpropyl)-[3- (1- methoxyl group -2- trimethyl first Silylation -1- sila -2- aza-cyclopentane) propyl] -1,3- propane diamine, three [3- (2,2- dimethoxy -1- azepine -2- silas Pentamethylene) propyl]-[3- (1- methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- the third two Amine, four (3- triethoxysilylpropyltetrasulfide) -1,3- propane diamine, three (3- triethoxysilylpropyltetrasulfide)-[3- (2,2- Diethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- propane diamine, bis- (3- triethoxysilylpropyltetrasulfides)-are bis- [3- (2,2- diethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- propane diamine, three [3- (2,2- diethoxy -1- nitrogen Miscellaneous -2- silacyclopentan) propyl]-(3- triethoxysilylpropyltetrasulfide) -1,3- propane diamine, four [3- (2,2- diethoxies - 1- azepine -2- silacyclopentan) propyl] -1,3- propane diamine, three (3- triethoxysilylpropyltetrasulfides)-[3- (1- ethyoxyl - 2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- propane diamine, bis- (3- triethoxysilyls third Base)-[3- (2,2- diethoxy -1- azepine -2- silacyclopentan) propyl]-[3- (1- ethyoxyl -2- trimethyl silyl - 1- sila -2- aza-cyclopentane) propyl] -1,3- propane diamine, bis- [3- (2,2- diethoxy -1- azepine -2- silacyclopentan) Propyl]-(3- triethoxysilylpropyltetrasulfide)-[3- (1- ethyoxyl -2- trimethyl silyl -1- sila -2- azacyclo- Pentane) propyl] -1,3- propane diamine, three [3- (2,2- diethoxy -1- azepine -2- silacyclopentan) propyl]-[3- (1- ethoxies Base -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- propane diamine, four (3- trimethyoxysilanes Base propyl) -1,3- double aminomethyl cyclohexanes, three (3- trimethoxy-silylpropyls)-[3- (2,2- dimethoxy -1- nitrogen Miscellaneous -2- silacyclopentan) propyl] -1,3- double aminomethyl cyclohexanes, bis- (3- trimethoxy-silylpropyls)-bis- [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- double aminomethyl cyclohexanes, three [3- (2,2- dimethoxies Base -1- azepine -2- silacyclopentan) propyl]-(3- trimethoxy-silylpropyl) -1,3- double aminomethyl cyclohexanes, four [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- propane diamine, three (3- trimethoxysilyls third Base) the double amino methyl rings of-[3- (1- methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- Hexane, bis- (3- trimethoxy-silylpropyls)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] - The double aminomethyl cyclohexanes of [3- (1- methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3-, Bis- [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl]-(3- trimethoxy-silylpropyl)-[3- (1- Methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- double aminomethyl cyclohexanes, three [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl]-[3- (1- methoxyl group -2- trimethyl silyl -1- sila - 2- aza-cyclopentane) propyl] the double aminomethyl cyclohexanes of -1,3-, four (3- triethoxysilylpropyltetrasulfide) -1,3- the third two Amine, three (3- triethoxysilylpropyltetrasulfides)-[3- (2,2- diethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- Bis- [3- (2,2- diethoxy -1- azepine -2- the silas of double aminomethyl cyclohexanes, bis- (3- triethoxysilylpropyltetrasulfides) - Pentamethylene) propyl] -1,3- double aminomethyl cyclohexanes, three [3- (2,2- diethoxy -1- azepine -2- silacyclopentan) third Base]-(3- triethoxysilylpropyltetrasulfide) -1,3- propane diamine, four [3- (2,2- diethoxy -1- azepine -2- silicon Polymorphs Alkane) propyl] -1,3- propane diamine, three (3- triethoxysilylpropyltetrasulfides)-[3- (1- ethyoxyl -2- trimethyl silyl - 1- sila -2- aza-cyclopentane) propyl] -1,3- double aminomethyl cyclohexanes, bis- (3- triethoxysilylpropyltetrasulfide)-[3- (2,2- diethoxy -1- azepine -2- silacyclopentan) propyl]-[3- (1- ethyoxyl -2- trimethyl silyl -1- sila - 2- aza-cyclopentane) propyl] -1,3- double aminomethyl cyclohexanes, bis- [3- (2,2- diethoxy -1- azepine -2- silicon Polymorphs Alkane) propyl]-(3- triethoxysilylpropyltetrasulfide)-[3- (1- ethyoxyl -2- trimethyl silyl -1- sila -2- azepine Pentamethylene) propyl] -1,3- double aminomethyl cyclohexanes, three [3- (2,2- diethoxy -1- azepine -2- silacyclopentan) third Base] the double amino methyl rings of-[3- (1- ethyoxyl -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] -1,3- Hexane, four (3- trimethoxy-silylpropyl) -1,6- hexamethylene diamines, five (3- trimethoxy-silylpropyl)-two sub- second Base triamine.

In above-mentioned formula (VI), as A by the modifying agent in the case where represented by above-mentioned formula (III), it can enumerate but unlimited In such as three (3- trimethoxy-silylpropyl)-methyl-1s, 3- propane diamine, bis- (2- trimethoxy-silylpropyls)- [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl]-methyl-1,3- propane diamine, bis- [3- (2,2- dimethoxies Base -1- azepine -2- silacyclopentan) propyl]-(3- trimethoxy-silylpropyl)-methyl-1,3- propane diamine, three (3- tri- Triethoxysilyl propyl)-methyl-1,3- propane diamine, bis- (2- triethoxysilylpropyltetrasulfide)-[3- (2,2- diethoxies Base -1- azepine -2- silacyclopentan) propyl]-methyl-1,3- propane diamine, bis- [3- (2,2- diethoxy -1- azepine -2- silas Pentamethylene) propyl]-(3- triethoxysilylpropyltetrasulfide)-methyl-1,3- propane diamine, N¹,N^1’(propane -1,3- diyl) is double (N¹Methyl-N³,N³Bis- (3- (trimethoxysilyl) propyl) -1,3- propane diamine), N¹(3- (bis- (3- (trimethoxies Silicyl) propyl) amino) propyl)-N¹Methyl-N³(3- (methyl (3- (trimethoxysilyl) propyl) amino) third Base)-N³(3- (trimethoxysilyl) propyl) -1,3- propane diamine.

In above-mentioned formula (VI), as A by the modifying agent in the case where represented by formula (IV), it can enumerate but be not limited to for example Four [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] silane, three [3- (2,2- dimethoxy -1- azepine -2- Silacyclopentan) propyl]-(3- trimethoxy-silylpropyl) silane, three [3- (2,2- dimethoxy -1- azepine -2- silicon Heterocycle pentane) propyl] it is-[3- (1- methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl] silane, double (3- trimethoxy-silylpropyl)-bis- [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] silane, (3- Trimethoxysilyl)-[3- (1- methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane)-bis- [3- (2, 2- dimethoxy -1- azepine -2- silacyclopentan) propyl] silane, bis- [3- (1- methoxyl group -2- trimethyl silyl -1- silicon Miscellaneous -2- aza-cyclopentane)-bis- [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] silane, three (3- trimethoxies Base silylpropyl)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] silane, bis- (3- trimethoxies Silylpropyl)-[3- (1- methoxyl group -2- trimethyl silyl -1- sila -2- aza-cyclopentane) propyl]-[3- (2, 2- dimethoxy -1- azepine -2- silacyclopentan) propyl] silane, bis- [3- (1- methoxyl group -2- trimethyl silyl -1- silicon Miscellaneous -2- aza-cyclopentane) propyl]-bis- (3- trimethoxy-silylpropyl) silane, bis- (3- trimethoxysilyls third Base)-bis- [3- (1- methoxyl group-2- methyl-1-sila-2- aza-cyclopentane) propyl] silane.

In above-mentioned formula (VI), as A by the modifying agent in the case where represented by above-mentioned formula (V), it can enumerate but be not limited to Such as 3- tri- [2- (2,2- dimethoxy -1- azepine -2- silacyclopentan) ethyoxyl] silicyl -1- (2,2- dimethoxy - 1- azepine -2- silacyclopentan) propane, 3- tri- [2- (2,2- dimethoxy -1- azepine -2- silacyclopentan) ethyoxyl] first silicon Alkyl -1- trimethoxysilylpropane.

It, can be with as the modifying agent for the organic group that A indicates to have oxygen atom and does not have reactive hydrogen in above-mentioned formula (VI) Enumerate such as (3- trimethoxy-silylpropyl)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] ether (4 function), 3,4,5- tri- (3- trimethoxy-silylpropyl)-cyclohexyl-[3- (2,2- dimethoxy -1- azepine -2- silicon Heterocycle pentane) propyl] ether (8 function).

It, can be with as the modifying agent for the organic group that A indicates to have phosphorus atoms and does not have reactive hydrogen in above-mentioned formula (VI) It enumerates but is not limited to such as (3- trimethoxy-silylpropyl) phosphate, bis- (3- trimethoxy-silylpropyl)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] phosphate, bis- [3- (2,2- dimethoxy -1- azepine -2- silicon Heterocycle pentane) propyl]-(3- trimethoxy-silylpropyl) phosphate, three [3- (2,2- dimethoxy -1- azepine -2- silicon Heterocycle pentane) propyl] phosphate.

In above-mentioned formula (VI), preferably A indicates above-mentioned formula (II) or above-mentioned formula (III), and k indicates 0.Thus appearance can be formed by having The tendency of the modifying agent easily obtained, and have after sulfide is made in the modified conjugated diene polymer of present embodiment Abrasion performance and the low more excellent tendency of magnetic hystersis loss performance.

As such modifying agent, it can enumerate but be not limited to for example bis- (3- trimethoxy-silylpropyl)-[3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] amine, three (3- trimethoxy-silylpropyl) amine, three (3- Triethoxysilylpropyltetrasulfide) amine, three (3- trimethoxy-silylpropyls)-[3- (2,2- dimethoxy -1- azepine -2- Silacyclopentan) propyl] -1,3- propane diamine, four [3- (2,2- dimethoxy -1- azepine -2- silacyclopentan) propyl] -1,3- Propane diamine, four (3- trimethoxy-silylpropyl) -1,3- propane diamine, four (3- trimethoxy-silylpropyl) -1,3- Double aminomethyl cyclohexanes, three (3- trimethoxy-silylpropyl)-methyl-1s, 3- propane diamine, bis- [3- (2,2- dimethoxies Base -1- azepine -2- silacyclopentan) propyl]-(3- trimethoxy-silylpropyl)-methyl-1,3- propane diamine.

It is preferred that A indicates that above-mentioned formula (II) or formula (III), k indicate in 0, above-mentioned formula (II) or formula (III) in above-mentioned formula (VI) A indicates 2~10 integer.The modified conjugated diene polymer of present embodiment has wear-resisting after sulfide is made as a result, Consumption and the more excellent tendency of low magnetic hystersis loss.

As such modifying agent, it can enumerate but be not limited to such as four [3- (2,2- dimethoxy -1- azepine -2- silas Pentamethylene) propyl] -1,3- propane diamine, four (3- trimethoxy-silylpropyl) -1,3- propane diamine, four (3- trimethoxy first Ethoxysilylpropyl) -1,3- double aminomethyl cyclohexanes, N¹(3- (bis- (3- (trimethoxysilyl) propyl) amino) third Base)-N¹Methyl-N³(3- (methyl (3- (trimethoxysilyl) propyl) amino) propyl)-N³(3- (trimethoxy first Silylation) propyl) -1,3- propane diamine.

The additive amount of the compound represented by the above-mentioned formula (VI) as modifying agent, conjugated diene can be polymerize The molal quantity of object relative to modifying agent molal quantity according to both making the side reacted with the ratio of desired stoichiometry Formula adjusts, and thus obtains the modified conjugated diene polymer with the desired degree of branching.

Specifically, the molal quantity of conjugated diene polymer is preferably 1.0 times moles relative to the molal quantity of modifying agent Above, 2.0 times moles or more are more preferably.In this case, in above-mentioned formula (VI), functional group number ((m-1) × i+ of modifying agent P × j+k) it is preferably 1~10 integer, more preferably 2~10 integer.

(hydrogenation process)

In the modified conjugated diene polymer of present embodiment, conjugated diene portion can be hydrogenated.To conjugation two The method that alkene portion is hydrogenated is not particularly limited, and can use well known method.

As suitable method for hydrogenation, it can enumerate and be blown into Gaseous Hydrogen into polymer solution in the presence of a catalyst Method.

As catalyst, for example, noble-metal-supported is urged in the catalyst of Porous inorganic substances etc. is heterogeneous Agent；Catalyst obtained from keeping the salt of nickel, cobalt etc. solubilized and reacting with organo-aluminium etc. has used urging for the metallocenes such as luxuriant titanium The homogeneous catalysts such as agent.Among these, from mild hydrogenation conditions aspect, preferably metallocene-titanium catalyst can be selected. In addition, the hydrogenation of aromatic series base can be carried out by using the supported catalyst of noble metal.

As hydrogenation catalyst, it can enumerate but be not limited to for example: (1) by Metal Supporteds such as Ni, Pt, Pd, Ru in carbon, oxygen Support type heteroge-neous catalyst made of SiClx, aluminium oxide, diatomite etc. are upper；(2) using the organic of Ni, Co, Fe, Cr etc. The so-called Ziegler-type hydrogenation catalyst of the reducing agents such as the transition metal salts such as hydrochlorate or acetylacetonate and organo-aluminium；(3)Ti, So-called metal-organic complex such as the organo-metallic compound of Ru, Rh, Zr etc. etc..In turn, it as hydrogenation catalyst, can also lift Such as Japanese Patent Publication 42-8704 bulletin, Japanese Patent Publication 43-6636 bulletin, Japanese Patent Publication 63-4841 public affairs out Report, Japanese Patent Publication 1-37970 bulletin, Japanese Patent Publication 1-53851 bulletin, Japanese Patent Publication 2-9041 bulletin, day The well known hydrogenation catalyst recorded in this Japanese Laid-Open Patent Publication 8-109219 bulletin.As preferred hydrogenation catalyst, can enumerate The reaction mixture of cyclopentadiene titanium compound and reproducibility organo-metallic compound.

In the manufacturing process of the modified conjugated diene polymer of present embodiment, after modified-reaction process, Ke Yigen Deactivator, neutralizer etc. are added into modified conjugated diene polymer solution according to needs.

As deactivator, it can enumerate but be not limited to such as water；Alcohol such as methanol, ethyl alcohol, isopropanol etc..

As neutralizer, can enumerate but be not limited to for example stearic acid, oleic acid, neodecanoic acid (carbon atom number be 9~11, The mixture of carboxylic acids of highly branched chain centered on 10) etc. carboxylic acids；Aqueous solution, the carbon dioxide of inorganic acid.

In the modified conjugated diene polymer of present embodiment, from prevent polymerization after generate gel in terms of and raising It sets out in terms of stability when processing, preferably addition rubber stabilizer.As rubber stabilizer, can be used well known Substance but it is not limited to following substance, such as can preferably enumerate 2,6- di-t-butyl -4- hydroxy-methylbenzene (BHT), positive 18 Bis- [(pungent sulfenyl) methyl] phenol of alkyl -3- (4 '-hydroxyls -3 ', 5 '-DI-tert-butylphenol compounds) propionic ester, 2- methyl -4,6- etc. are anti- Oxidant.

In order to further improve present embodiment modified conjugated diene polymer processability, can according to need to Addition filling oil in modified conjugated diene copolymer.

As the method for the addition filling oil into modified conjugated diene polymer, it is preferably but not limited to following methods: to Addition filling is oily in the solution of modified conjugated diene polymer and is mixed, and oil filling copolymer solution is made, later to it Carry out desolventizing.

As filling oil, it can enumerate but be not limited to such as aromatic oil, naphthenic oil, paraffin oils.Among these, from The aspect of Environmental security and prevent oil leak and wetland grab ground characteristic in terms of set out, be preferably based on the polycyclic fragrance of IP346 method Race's (PCA) ingredient is 3 mass % substitution aromatic oil below.As substitution aromatic oil, Kautschuk Gummi can be enumerated TDAE shown in Kunststoffe 52 (12) 799 (1999) (Treated Distillate Aromatic Extracts, Processed distillation aromatic extract), MES (Mild Extraction Solvate, the solvate mildly extracted) etc., with And RAE (Residual Aromatic Extracts, remaining aromatic extract).

The additive amount of filling oil is not particularly limited, it is preferred relative to 100 mass parts of modified conjugated diene polymer For more than 10 mass parts 60 below the mass, it is more than more preferably 20 mass parts 37.5 below the mass.

As the method for the modified conjugated diene polymer for obtaining present embodiment from polymer solution, can be used Well known method.For example: after being separated solvent using stripping etc., polymer is filtered out, further it is taken off Water and drying, the method for obtaining polymer；It is concentrated using flash tank, further carries out devolatilization using degassing extruder etc. Method；The method of devolatilization is directly carried out using whizzer etc..

(manufacture of the modified conjugated diene polymer based on blending)

In the manufacturing process of the modified conjugated diene polymer of present embodiment, by high in degree of modification height, molecular weight Polymer in the suitably low polymer of mixed and modified rate low (or unmodified), molecular weight, can prepare meet it is of the invention The polymer of feature.

The polymer high as degree of modification, molecular weight is high, for example, degree of modification is 50%~90%, Weight-average molecular Amount is 25 × 10⁴Above 350 × 10⁴Polymer below.

The polymer of low molecular weight as unmodified (or degree of modification is low), for example, degree of modification be 0%~ 60%, weight average molecular weight is 10 × 10⁴Above 150 × 10⁴Polymer below.

The weight average molecular weight (MwH) of the polymer high about degree of modification height, molecular weight is low with degree of modification, molecular weight is low gathers Close object weight average molecular weight (MwL) ratio, MwL divided by value obtained from MwH (MwL/MwH) be preferably 0.1 or more 0.8 with Under, more preferably 0.2 or more 0.7 or less, further preferably 0.3 or more 0.6 or less.Above-mentioned (MwL/MwH) is 0.1 or more It is low with adhesion when vulcanization in metal surface in processing in 0.8 situation below, there is high abrasion after sulfide is made Consumption.

When being blended, the quality (WH) and degree of modification of the polymer high about degree of modification, molecular weight is high are low, molecular weight is low The ratio (mass fraction) of the quality (WL) of polymer, WL are preferred relative to ratio (WL)/(WH+WL) of gross mass (WH+WL) It is 0.1 or more 0.8 or less, more preferably 0.15 or more 0.6 or less, further preferably 0.2 or more 0.5 or less.The value is 0.1 It is low with adhesion when vulcanization in metal surface in processing in above 0.8 situation below, there is height after sulfide is made Abrasion performance.

The blend method of polymer is not particularly limited, following methods can be enumerated: two kinds of polymer being made molten The method being dried after liquid and mixing；Solution is made in a kind of polymer, another polymer (solid) is added, solution is made And it is mixed, the method being dried later；Two kinds of polymer is mixed with solid-like, by utilizing roller or extruder progress Melting mixing and mixed method preferably two kinds of polymer is made molten from obtaining uniform mixture aspect The method being dried after liquid and mixing is preferably mixed two kinds of polymer with solid-like from energy efficiency aspect, is led to It crosses and carries out melting mixing using roller or extruder come mixed method.

[polymer composition]

The polymer composition of present embodiment includes the modified conjugated diene of the present embodiment of 10 mass % or more Polymer.

The polymer composition of present embodiment may include other than the modified conjugated diene polymer of present embodiment Polymer.As the polymer other than the modified conjugated diene polymer of the present embodiment, it is poly- that rubber-like can be enumerated Close object or resinous polymer.

As the rubber-like polymer other than the modified conjugated diene polymer of present embodiment, can enumerate but unlimited It is total in such as conjugated diene polymer or the random of its hydride, conjugated diene based compound and vinyl aromatic compounds It is polymers or its hydride, the block copolymer of conjugated diene based compound and vinyl aromatic compounds or its hydride, non- Diene polymer, natural rubber.

As specific rubber-like polymer, such as butadiene rubber or its hydride, isoamyl can be enumerated but are not limited to Diene rubber or its hydride, SBR styrene butadiene rubbers or its hydride, styrene-butadiene block copolymer or its hydrogen The styrene series elastomers such as compound, styrene-isoprene block copolymer or its hydride, nitrile rubber or its hydride.

As above-mentioned non-diene polymer, it can enumerate but be not limited to such as ethylene-propylene rubber, ethylene-propylene-two The olefin-based of alkene rubber, Ethylene/Butylene-diene rubber, ethylene butylene rubber, polyethylene-hexene rubber, Ethylene-octene rubber etc. Elastomer, butyl rubber, brombutyl, acrylic rubber, fluorubber, silicone rubber, chlorinated polyethylene rubber, epoxy chlorine Propane rubber, 'alpha ', ' bela '-unsaturated nitrile-acrylate-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber.

As above-mentioned natural rubber, it can enumerate but be not limited to for example as RSS3~No. 5 of smoke sheet rubber, SMR, epoxidation Natural rubber.

Gather as by the modified conjugated diene of the modified conjugated diene polymer of present embodiment and present embodiment The mixed method that the polymer (referred to as other polymers) other than object is mixed to get polymer composition is closed, can be enumerated modification Method that the solution of conjugated diene polymer is mixed with the solution of other polymers, by modified conjugated diene polymer and its The various methods such as the method for his polymer machinery mixing.

Above-mentioned other polymers, which can be, imparts the modified rubber that hydroxyl, amino etc. have polar functional group.

In the case where using the polymer composition of present embodiment as tire materials'use, as other polymers, It is preferable to use butadiene rubber, isoprene rubber, SBR styrene butadiene rubbers, natural rubber, butyl rubbers.

In the case that other polymers are rubber-like polymer, from the balance aspect of performance and processing characteristics, Weight average molecular weight is preferably 2,000 or more 2,000,000 or less, more preferably 5,000 or more 1,500,000 or less.In addition also Rubber-like polymer, the i.e. so-called liquid rubber of low molecular weight can be used.These rubber-like polymers can be used alone one Kind, can also share it is two or more.

In the polymer of the manufacture modified conjugated diene polymer comprising present embodiment and other rubber-like polymers In the case where composition (rubber composition), the modified conjugated diene polymer of present embodiment is poly- relative to other rubber-like The content ratio (mass ratio) (modified conjugated diene polymer/other rubber-like polymers) for closing object is preferably 10/90 or more 100/0 or less, it is more preferably 20/80 or more 90/10 or less, further preferably 50/50 or more 80/20 or less.

Therefore, total amount (100 matter in the polymer composition of present embodiment, relative to the polymer composition Measure %), the modified conjugated diene polymer of present embodiment preferably comprises 10 mass % or more, 100 mass % or less, more excellent Choosing contains 20 mass % or more, 90 mass % or less, further preferably 50 mass % or more, 80 mass % or less.

When the mass ratio of (modified conjugated diene polymer/other rubber-like polymers) is above range, sulphur is made The balancing good of low magnetic hystersis loss and anti-slippery after compound, abrasion performance and breakdown strength are also satisfactory.

The modified conjugated diene polymer of present embodiment is suitable as sulfide use.As sulfide, Ke Yiju Out for example tire, hose, sole, vibration-proof rubber, automobile component, exempt from shake rubber, in addition it can enumerate impact resistance polyphenyl second The resin tooths rubber such as alkene, ABS resin.

Modified conjugated diene polymer is especially suitable for the composition of tire tread-rubber.Sulfide for example can be with It obtains as follows: by the modified conjugated diene polymer of present embodiment and silicon oxide series inorganic filler, carbon black when necessary Equal inorganic fillers, present embodiment modified conjugated diene polymer other than rubber-like polymer, silane coupling agent, rubber Glue softening agent, vulcanizing agent, vulcanization accelerator, vulcanization aid etc. are kneaded, and after rubber composition is made, heating carries out sulphur Change, thus obtains the sulfide.

[rubber composition comprising filler]

The rubber composition of present embodiment includes: 100 mass parts of rubber-like polymer, the rubber-like polymer contain 10 The modified conjugated diene polymer of the present embodiment of quality % or more；And 5~150 mass parts of filler.

In addition, the filler preferably comprises silicon oxide series inorganic filler.

In rubber composition, by dispersing silicon oxide series inorganic filler, processability when with manufacture sulfide is more Excellent tendency has the balancing good of low magnetic hystersis loss and anti-slippery, breakdown strength and wear-resisting after sulfide is made The more excellent tendency of consumption.

The rubber composition of present embodiment is for vulcanized rubbers purposes such as automobile components, the shoes such as tire, vibration-proof rubber In the case where it is also preferred that including silicon oxide series inorganic filler.

As filler, it can enumerate but be not limited to such as silicon oxide series inorganic filler, carbon black, metal oxide, gold Belong to hydroxide.Among these, preferred silicon oxide series inorganic filler.These fillers can be used alone, and can also close With two or more.

Relative to 100 mass parts of rubber-like polymer of the modified conjugated diene polymer comprising present embodiment, originally The content of filler in the rubber composition of embodiment be 5.0 mass parts or more 150 below the mass, preferably 10 mass Part or more 120 below the mass, it is more than more preferably 20 mass parts that 100 below the mass.

About the content of filler, from embody the additive effect aspect of filler for 5.0 mass parts more than, from Make filler is fully dispersed, make rubber composition processability and mechanical strength in practical adequately aspect set out as 150 matter Measure part or less.

It is not particularly limited as silicon oxide series inorganic filler, well known substance can be used, preferably comprise SiO₂Or Si₃Solid particle of the Al as structural unit more preferably includes SiO₂Or Si₃Solid of the Al as the principal component of structural unit Grain.Herein, principal component refer in silicon oxide series inorganic filler containing 50 mass % or more, preferably comprise 70 mass % with Upper, further preferably 80 mass % or more ingredients.

As silicon oxide series inorganic filler, it can enumerate but be not limited to such as silica, clay, talcum, mica, diatom The inorganic fibrous substance such as soil, wollastonite, montmorillonite, zeolite, glass fibre.

The silicon oxide series inorganic filler of hydrophobization, silicon oxide series inorganic filler have been carried out in addition it can enumerate surface With the mixture of the inorganic filler other than silicon oxide series.

Among these, from intensity and abrasion performance etc., preferably silica and glass fibre, more preferably aoxidize Silicon.

As silica, it can enumerate but be not limited to such as dry oxidation silicon, wet oxidation silicon, synthetic silicate oxidation Silicon.In these silica, from the improvement of destruction characteristic and the balancing good aspect of anti-slippery, preferably wet type Silica.

In the rubber composition of present embodiment, from obtain practical good abrasion performance and destruction characteristic in terms of go out Hair, the N2 adsorption specific surface area that silicon oxide series inorganic filler is found out by BET absorption method is preferably 100m²/ g or more 300m²/ g with Under, more preferably 170m²/ g or more 250m²/ g or less.In addition, as needed, specific surface area is smaller (such as table can be compared Area is less than 200m²/ g) silicon oxide series inorganic filler and bigger (for example, 200m of specific surface area²/ g or more) oxidation Silicon systems inorganic filler is applied in combination.

Especially using bigger (for example, 200m of specific surface area²/ g or more) silicon oxide series inorganic filler when, The dispersibility of silica is improved, and abrasion performance can be effectively improved, and having can be such that good destruction characteristic and low magnetic hysteresis damages The tendency that consumption highly balances.

Relative to 100 mass parts of rubber-like polymer comprising modified conjugated diene polymer, the rubber of present embodiment The content of silicon oxide series inorganic filler in glue composition is preferably 5.0 mass parts or more, 150 mass parts, more preferably 10 matter Measure part or more 120 below the mass, it is more than further preferably 20 mass parts 100 below the mass.

About the content of silicon oxide series inorganic filler, from embodying additive effect aspect preferably 5.0 mass Part or more, from making, its is fully dispersed, making the processability of rubber composition and mechanical strength, adequately aspect is excellent in practical It is selected as 150 below the mass.

As carbon black, the carbon black of each grade such as SRF, FEF, HAF, ISAF, SAF can be enumerated but is not limited to.These Among, preferably N2 adsorption specific surface area is 50m²/ g or more and dibutyl phthalate (DBP) oil absorption are 80mL/100g Carbon black below.

Relative to 100 mass parts of rubber-like polymer comprising modified conjugated diene polymer, the content of carbon black is preferred For more than 0.5 mass parts 100 below the mass, it is more than more preferably 3.0 mass parts 100 below the mass, further preferably It is more than 5.0 mass parts that 50 below the mass.

About the content of carbon black, from dry grip performance, electric conductivity etc. is embodied in the performance required on the way such as tire Aspect set out more than preferably 0.5 mass parts, below the mass from the aspect preferably 100 of dispersibility.

Metal oxide refer to chemical formula MxOy (M indicates metallic atom, x and y each independently represent 1~6 it is whole Number) as structural unit principal component solid particle.As metal oxide, can enumerate but be not limited to such as aluminium oxide, Titanium oxide, magnesia, zinc oxide.

As metal hydroxides, it can enumerate but be not limited to such as aluminium hydroxide, magnesium hydroxide, zirconium hydroxide.

The rubber composition of present embodiment may include silane coupling agent.Silane coupling agent have make rubber-like polymer Interaction with filler becomes close function, especially has inorganic for rubber-like polymer and silicon oxide series respectively The compatibility of filler or binding affinity group have sulphur bonded portion and alkoxysilyl preferably in a molecule Or the compound of silanol group part.

As such compound, it can be cited for example that bis- [3- (triethoxysilyl)-propyl]-tetrasulfides, Double-[3- (triethoxysilyl)-propyl]-disulphide, double-[2- (triethoxysilyl)-ethyl]-four vulcanize Object.

Relative to above-mentioned 100 mass parts of filler, the content of silane coupling agent is preferably 0.1 mass parts or more, 30 mass parts Below, be more preferably 0.5 mass parts or more 20 below the mass, it is more than further preferably 1.0 mass parts 15 below the mass. When the content of silane coupling agent is above range, having can make more significantly to be inclined by silane coupling agent bring additive effect To.

In the rubber composition of present embodiment, from the improvement aspect for seeking its processability, rubber may include Use softening agent.

As softener of rubber, the synthesis softening agent of mineral oil or liquid or low molecular weight is suitable.

For the softening of rubber, increase-volume and processability raising and being referred to as using operates oil or extending oil Mineral oil system softener of rubber is the mixture of aromatic ring, cycloalkanes hydrocarbon ring and alkane hydrocarbon chain, the carbon atom of alkane hydrocarbon chain The substance that number accounts for 50% or more in whole carbon is referred to as alkane hydrocarbon system, cycloalkane ring carbon atom number accounted in whole carbon 30% with Upper 45% substance below is referred to as cycloalkanes hydrocarbon system, and the substance that aromatic carbon atoms number accounts in whole carbon more than 30% is referred to as Aromatic system.

The modified conjugated diene polymer of present embodiment is conjugated diene compound and vinyl aromatic compounds Copolymer in the case where, as used softener of rubber, in right amount containing the softener of rubber of aromatic compound Tend to well with the amalgamation of copolymer, thus is preferred.

Relative to 100 mass parts of rubber-like polymer containing modified conjugated diene polymer, softener of rubber Content be preferably 0 mass parts or more 100 below the mass, more preferably it is more than 10 mass parts 90 below the mass, it is further excellent It is selected as 30 mass parts or more 90 below the mass.

By having the content of softener of rubber below the mass, relative to 100 mass parts 100 of rubber-like polymer Have the tendency that can inhibit exudation, the rubber composition surface for inhibiting present embodiment it is sticky.

About by modified conjugated diene polymer and other rubber-like polymers, silicon oxide series inorganic filler, carbon black And the method that the additives such as other fillers, silane coupling agent, softener of rubber are mixed, it can enumerate but be not limited to example It is such as usual using open mill, Banbury, kneader, single screw extrusion machine, double screw extruder, multi-screw extruder Mixing machine melting mixing method；After the dissolution mixing of each ingredient, the method for heating removing solvent.In these methods, from life It sets out in terms of yield, excellent mixing, the melting carried out preferably by roller, Banbury, kneader, extruder is mixed Refining method.

Rubber-like polymer and other fillers, silane coupling agent and additive are disposably mixed in addition it can application Any method in the method for refining, the method mixed in several times.

The vulcanising composition that vulcanizing treatment is implemented using vulcanizing agent can be made in the rubber composition of present embodiment.

As vulcanizing agent, it can enumerate but be not limited to the initiation of the free radical such as organic peroxide and azo-compound Agent, oxime compound, nitroso compound, polyhydric amine compounds, sulphur, sulfur-containing compound.In sulfur-containing compound include sulfur monochloride, Sulfur dichloride, di-sulphide compounds, macromolecule polysulfide etc..

Relative to 100 mass parts of rubber constituent, the content of vulcanizing agent be preferably 0.01 mass parts or more 20 below the mass, It is more than more preferably 0.1 mass parts that 15 below the mass.

As vulcanization process, conventionally known method can be applied, curing temperature be preferably 120 DEG C or more 200 DEG C or less, More preferably 140 DEG C or more 180 DEG C or less.

In vulcanization, can according to need using vulcanization accelerator.As vulcanization accelerator, can be used conventionally known Material can be enumerated but be not limited to such as sulfenamide system, guanidine system, thiuram system, aldehyde-amine system, aldehyde-ammonia system, thiazole system, thiocarbamide System, dithiocarbamate system vulcanization accelerator.In addition, as vulcanization aid, such as zinc white, hard can be enumerated but is not limited to Resin acid.Relative to 100 mass parts of rubber constituent, the content of vulcanization accelerator be preferably 0.01 mass parts or more, 20 mass parts with Under, more preferably it is more than 0.1 mass parts 15 below the mass.

It is interior in the range of without detriment to the purpose of present embodiment in the rubber composition of present embodiment, it can make With other softening agents other than the above and filler, heat-resisting stabilizing agent, antistatic agent, weathering stabilizers, age resister, coloring The various additives such as agent, lubricant.

As other softening agents, well known softening agent can be used.As other fillers, specifically, can enumerate Calcium carbonate, magnesium carbonate, aluminum sulfate, barium sulfate.As above-mentioned heat-resisting stabilizing agent, antistatic agent, weathering stabilizers, age resister, Well known material can be used in colorant, lubricant respectively.

[tire]

The rubber composition for the modified conjugated diene polymer for containing present embodiment is suitable with material as tire 's.

The rubber composition for tire of present embodiment can be applied to but be not limited to for example save oil consumption tire, four seasons type wheel Each position of tires such as tyre surface, carcass, tyre bead, bead portion of the various tires such as tire, high-performance tire, studless tire In.

Especially sulphur is being made in the rubber composition for tire of the modified conjugated diene polymer containing present embodiment The balance and excellent wear resistance of low magnetic hystersis loss and anti-slippery after compound, thus it is more suitable as province's oil consumption wheel The tyre surface purposes of tire, high-performance tire.