TW201738282A - Silane-modified hydrocarbon resin and elastomer composition for tire - Google Patents

Abstract

A main object of the present invention is to provide a silane-modified hydrocarbon resin that gives an elastomer composition for a tire with excellent processability and balance of rolling resistance and wet grip properties. The object is attained by providing a silane-modified hydrocarbon resin obtained by, with 0.1% by mass to 10% by mass of an organic silane compound represented by the following formula (1), modifying 100% by mass of a hydrocarbon resin including 20% by mass to 70% by mass of a 1,3-pentadien monomer unit, 10% by mass to 35% by mass of a C4 to C6 alicyclic monoolefin monomer unit, 3% by mass to 30% by mass of a C4 to C8 acyclic monoolefin monomer unit, 0% by mass to 10% by mass of an alicyclic diolefin monomer unit, and 0% by mass to 40% by mass of an aromatic monoolefin monomer unit, characterized in that the weight average molecular weight (Mw) is in a range of 1000 to 8000, Z average molecular amount (Mz) is in a range of 2000 to 25000, the ratio of the Z average molecular amount per the weight average molecular weight (Mz/Mw) is in a range of 1.0 to 4.5, and the softening point temperature is in a range of 80 DEG C to 110 DEG C.

Description

Hydroxyl resin modified by decane and elastomer composition for tire

The present invention relates to a decane-modified hydrocarbon resin which can impart an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

In recent years, in terms of automobile tires, there is a strong demand for low fuel economy due to environmental problems and resource problems. On the other hand, from the viewpoint of safety, for example, there is a demand for improvement in grip when wet. a crosslinked product of an elastomer composition in which an elastomer is blended with cerium oxide as a filler, and a rolling resistance of the former in the case of constituting a tire, compared to a crosslinked product of an elastomer composition blended with carbon black small. Therefore, by using a crosslinked product of an elastomer composition in which cerium oxide is blended to form a tire, a tire excellent in low fuel economy can be obtained.

However, even if the cerium oxide is blended in the conventional elastomer, since the affinity between the elastomer and the cerium oxide is insufficient, the separation is easy, and therefore the elastomer composition before crosslinking has poor workability and will be The crosslinked body of the elastomer obtained by crosslinking the article may have a problem of insufficient rolling resistance in the case of constituting the tire.

Moreover, in the patent document 1, it is disclosed for the purpose of improving the rolling resistance of a tire and the grip of wetness, and mixing the decane-modified hydrocarbon resin to an elastomer.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-4074

However, in the decane-modified hydrocarbon resin described in Patent Document 1, when a tire is produced by using an elastomer crosslinked product obtained by adding such a material, it is difficult to uniformly improve wet grip and rolling. The problem of two characteristics of resistance.

The present invention has been made in view of the above problems, and a main object thereof is to provide a decane-modified hydrocarbon resin which can impart an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance. .

The inventors of the present invention conducted a careful review of the decane-modified hydrocarbon resin of the elastomer composition for tires which is excellent in workability and has a good balance between rolling resistance and wet grip performance, and found that the next Further, the present invention has been completed. For example, a conventional decane-modified hydrocarbon resin as disclosed in Patent Document 1 has a glass transition temperature (Tg) and a weight average molecular weight (Mw), and the reduction in rolling resistance is Associated with.

According to the present invention, there is provided a hydrocarbon resin modified with decane, which is characterized in that it is contained in an amount of 0.1 part by mass to 10 parts by mass based on the organodecane compound represented by the following formula (1). 20% by mass to 70% by mass of the olefin monomer unit, 10% by mass to 35% by mass of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, and 3 parts by weight of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms 100% by mass of the alicyclic diene monomer unit, 0% by mass to 10% by mass, and 100 parts by mass of the hydrocarbon resin of 0% by mass to 40% by mass of the aromatic monoolefin monomer unit are modified. The weight average molecular weight (Mw) is in the range of 1000 to 8000, the Z average molecular weight (Mz) is in the range of 2000 to 25000, and the ratio of the Z average molecular weight to the weight average molecular weight (Mz/Mw) is in the range of 1.0 to 4.5. The softening point temperature is in the range of 80 ° C to 110 ° C.

X ₃ Si-RF-[R-Si-X ₃ ] _p (1)

(In the formula (1), each of the X systems is independently a helium atom-bonding functional group, and each of the R systems is independently, and is a divalently substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, and F is 1 or more. The organic functional group of the valence, when F is 1 valence, p is 0, and when F is multivalent, p is at least 1).

Preferably, the above X is a hydroxyl group or R ¹ -O- (wherein R ¹ is an alkyl group, an alkoxyalkyl group, an aryl group, an arylalkyl group or a cycloalkyl group of 20 carbon atoms), R Is an alkyl group, p is 0 or 1, when p is 0, F is selected from the group consisting of an amine group, a guanamine group, a hydroxyl group, an alkoxy group, a halogen group, a thio group, a hydrazine group, a carboxyl group, a fluorenyl group. , vinyl, allyl, styryl, ureido, epoxy, isocyanate, decyl, epoxypropoxy, and propylene fluorenyl, when p is 1, F is a sulfur atom 2~ 20 of the two-valent polysulfide base.

Moreover, according to the present invention, a tire bomb can be provided The morphological composition is characterized by comprising at least one elastomer, at least one filler, and the above-mentioned decane-modified hydrocarbon resin.

Preferably, the filler is cerium oxide.

According to the present invention, it is possible to provide a decane-modified hydrocarbon resin which can impart an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The present invention relates to a hydrocarbon resin modified with decane and an elastomer composition for a tire using the same.

Hereinafter, the decane-modified hydrocarbon resin of the present invention and the elastomer composition for a tire will be described in detail.

A. Hydrocarbon resin modified by decane

The decane-modified hydrocarbon resin of the present invention is characterized in that it contains 20 parts by mass of the 1,3-pentadiene monomer unit by using 0.1 to 10 parts by mass of the organodecane compound represented by the following formula (1). ~70% by mass, carbon number 4-6 alicyclic monoolefin monomer unit 10% by mass to 35% by mass, carbon number 4-8, acyclic monoolefin monomer unit 3% by mass to 30% by mass, fat When the cyclic diene monomer unit is 0% by mass to 10% by mass, and the aromatic monoolefin monomer unit is 0% by mass to 40% by mass, 100 parts by mass of the hydrocarbon resin is modified, and the weight average molecular weight (Mw) is In the range of 1000 to 8000, the Z average molecular weight (Mz) is in the range of 2000 to 25000, and the ratio of the Z average molecular weight to the weight average molecular weight (Mz/Mw) is 1.0 to 4.5. Within the circumference, the softening point temperature is in the range of 80 ° C to 110 ° C.

X ₃ Si-RF-[R-Si-X ₃ ] _p (1)

(In the formula (1), each of the X systems is independently a helium atom-bonding functional group, and each of the R systems is independently, and is a divalently substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, and F is 1 or more. The organic functional group of the valence, when F is 1 valence, p is 0, and when F is multivalent, p is at least 1).

According to the present invention, the decane-modified hydrocarbon resin is modified with a predetermined amount of an organic decane compound to modify a hydrocarbon resin containing the above-mentioned predetermined monomer unit in a predetermined ratio, and has a predetermined weight average molecular weight and a Z average molecular weight. By the characteristics of the ratio of the Z average molecular weight to the weight average molecular weight and the conversion point temperature, it is possible to obtain an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

Here, the reason for obtaining the elastomer composition for a tire excellent in workability and excellent in balance between rolling resistance and wet grip performance is not clear, but it is considered to be as follows by using the above-described decane-modified hydrocarbon resin. Said.

That is, since it is a hydrocarbon resin using the above-mentioned predetermined monomer unit and ratio and further having the above-mentioned predetermined characteristics, the decane-modified hydrocarbon resin of the present invention can be suitably used as a weight average molecular weight (Mw) and a glass transition temperature. The lower one.

Therefore, the hydrocarbon resin modified by decane of the present invention can be excellent in compatibility with an elastomer when it is mixed with an elastomer or the like to form an elastomer composition, for example, the obtained elastomer composition. In other words, the loss coefficient tan δ of the crosslinked product at 60 ° C can be moderately reduced, and can be appropriately increased. Its loss factor tan δ at 0 °C.

As a result, when a tire is manufactured using such an elastomer composition, a tire having excellent balance between rolling resistance and wet grip performance can be formed.

In addition, since the hydrocarbon resin modified by the decane is excellent in compatibility with the elastomer, for example, it is easy to uniformly mix the elastomer with the elastomer, and therefore it is excellent in processing properties.

Further, since the above-mentioned decane-modified hydrocarbon resin is modified with a predetermined amount of an organic decane compound and contains a predetermined amount of a decane-modified portion, it can be increased by, for example, increasing the dispersibility of cerium oxide. The appearance surface area of cerium oxide promotes the combination of the elastomer and cerium oxide, and reduces the loss coefficient tan δ at 60 ° C, so that an elastomer composition excellent in rolling resistance can be obtained.

As described above, the above-described decane-modified hydrocarbon resin obtained by modifying a hydrocarbon resin containing a predetermined monomer unit in a predetermined ratio by using a predetermined amount of an organic decane compound can impart excellent workability and rolling resistance and wet grip performance. A well-balanced elastomer composition for tires.

The decane-modified hydrocarbon resin-based hydrocarbon resin of the present invention is a modified product obtained from an organic decane compound.

In the following, a hydrocarbon resin (hereinafter sometimes referred to simply as a pre-modification resin) which is modified by an organic decane compound, an organic decane compound which has been modified by a hydrocarbon resin, and a hydrocarbon resin which has been modified with decane (hereinafter sometimes referred to simply as Modified resin) will be described in detail.

Hydrocarbon resin

The above hydrocarbon resin is a raw material resin before being modified by an organic decane compound, and comprises a 1,3-pentadiene monomer unit of 20% by mass to 70% by mass. %, the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, 10% by mass to 35% by mass, and the acyclic monoolefin monomer unit having 4 to 8 carbon atoms, 3 to 30% by mass, and alicyclic two The olefin monomer unit is 0% by mass to 10% by mass, and the aromatic monoolefin monomer unit is 0% by mass to 40% by mass.

Further, the content ratio of the above monomer unit is the same as that of the modified resin, and the preferable range of the content ratio is also the same as that of the pre-modification resin.

The content of the 1,3-pentadiene monomer unit in the pre-modification resin may be in the range of 20% by mass to 70% by mass, preferably in the range of 25% by mass to 69% by mass, wherein It is preferably in the range of 30% by mass to 68% by mass, and particularly preferably in the range of 35% by mass to 67% by mass. When the above-mentioned content is within the above range, the decane-modified hydrocarbon resin of the present invention can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

Further, the cis/trans isomer ratio in the 1,3-pentadiene may be any ratio and is not particularly limited.

The alicyclic monoolefin having 4 to 6 carbon atoms has a hydrocarbon compound having 4 to 6 carbon atoms in the molecular structure of one ethylenically unsaturated anthracene and a non-aromatic ring structure. Specific examples of the alicyclic monoolefin having 4 to 6 carbon atoms include cyclobutene, cyclopentene, cyclohexene, methylcyclobutene, and methylcyclopentene.

The content of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms in the pre-modification resin may be in the range of 10% by mass to 35% by mass, preferably 13% by mass to 34% by mass. In the range, it is preferably in the range of 16% by mass to 32% by mass, and particularly preferably in the range of 19% by mass to 30% by mass. Because the above content is within the above range, the scripture of the present invention The alkane-modified hydrocarbon resin can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

Further, the alicyclic monoolefin having 4 to 6 carbon atoms may be any ratio corresponding to each of the compounds, and is not particularly limited, and preferably contains at least cyclopentene, and cyclopentene The proportion of the alicyclic monoolefin having 4 to 6 carbon atoms is more preferably 50% by mass or more.

The acyclic monoolefin having 4 to 8 carbon atoms has a chain hydrocarbon compound having 4 to 8 carbon atoms and having no ring structure in its molecular structure. Specific examples of the acyclic monoolefin having 4 to 8 carbon atoms include butenes such as 1-butene, 2-butene and isoprene (2-methylpropene); 1-pentene; 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene and the like pentene; 1-hexene, 2-hexene, 2 a hexene such as methyl-1-pentene; a heptene such as 1-heptene, 2-heptene or 2-methyl-1-hexene; 1-octene, 2-octene, 2-methyl Octenes such as -1-heptene, diisobutylene (2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-1-pentene).

The content of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms in the pre-modification resin may be in the range of 3% by mass to 30% by mass, preferably 3% by mass to 25% by mass. In the range, it is preferably in the range of 3 mass% to 22 mass%, and particularly preferably in the range of 3 mass% to 20 mass%. When the above-mentioned content is within the above range, the decane-modified hydrocarbon resin of the present invention can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

Further, in the case of the acyclic monoolefin having 4 to 8 carbon atoms, the ratio of each compound (including the isomer) corresponding thereto may be any ratio, and is not particularly limited, but preferably contains at least 2 -methyl-2-butene, different At least one selected from the group consisting of pentadiene and diisobutylene, more preferably 2-methyl-2-butene, isoprene and diisobutylene in an acyclic monoolefin having 4 to 8 carbon atoms The proportion in the middle is 50% by mass or more.

The pre-modified resin may also contain an alicyclic diene in its raw material.

The alicyclic diolefin is a hydrocarbon compound having two or more ethylenically unsaturated bonds and a non-aromatic ring structure in its molecular structure. Specific examples of the alicyclic diene include a polymer of cyclopentadiene such as cyclopentadiene or dicyclopentadiene, and a polymer of methylcyclopentadiene or methylcyclopentadiene. . The content of the alicyclic diene monomer unit in the pre-modification resin may be in the range of 0% by mass to 10% by mass, preferably in the range of 0% by mass to 7% by mass, wherein It is preferably in the range of 0% by mass to 5% by mass, and particularly preferably in the range of 0% by mass to 3% by mass. When the above-mentioned content is within the above range, the decane-modified hydrocarbon resin of the present invention can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The pre-modification resin may also contain an aromatic monoolefin monomer unit in its raw material.

The aromatic monoolefin is an aromatic compound having one ethylenic unsaturated bond in its molecular structure. Specific examples of the aromatic monoolefin include styrene, α-methylstyrene, vinyltoluene, anthracene, and coumarone.

The content of the aromatic monoolefin monomer unit in the pre-modification resin may be in the range of 0% by mass to 40% by mass, preferably in the range of 0% by mass to 35% by mass, wherein 0 Mass%~30% by mass It is preferably in the range, and is particularly preferably in the range of 0% by mass to 28% by mass. When the above-mentioned content is within the above range, the decane-modified hydrocarbon resin of the present invention can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

In the range of a modified hydrocarbon resin capable of imparting an elastomer composition for a tire which is excellent in workability and excellent in rolling resistance and wet grip performance, the pre-modified resin contains 1,3-pentadiene in addition to 1,3-pentadiene. Monomer unit, alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, acyclic monoolefin monomer unit having 4 to 8 carbon atoms, alicyclic diene monomer unit, and aromatic monoolefin monomer In addition to the unit, other monomer units may also be included.

The other monomer used for constituting such another monomer unit is, for example, a compound having addition polymerization which is addition polymerization of 1,3-pentadiene or the like other than the above monomer, and is not particularly limited. The above other monomers, such as 1,3-pentadiene, 1,2-butadiene, isoprene, 1,3-hexadiene, 1,4-pentadiene, etc. An unsaturated hydrocarbon having 4 to 6 carbon atoms other than an alkene; an alicyclic monoolefin having 7 or more carbon atoms such as a cycloheptene; and an acyclic monoolefin having a carbon number of 4 to 8 such as ethylene, propylene or decene.

Here, the content of the other monomer unit in the pre-modification resin in the pre-modification resin may be a modified hydrocarbon resin having the above-described predetermined characteristics, and specifically, it is usually 0% by mass to 30% by mass. Within the range of %, it is preferably in the range of 0% by mass to 25% by mass, more preferably in the range of 0% by mass to 20% by mass. The decane-modified hydrocarbon resin of the present invention can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The method of manufacturing the pre-modification resin is as long as it is The polymerizable component (monomer mixture A) which is a monomer of the above monomer unit is not particularly limited as long as it is appropriately subjected to addition polymerization. For example, a pre-modification resin can be obtained by addition polymerization using a Friedel-Crafts cationic polymerization catalyst. As a method suitable for use in the production of the pre-modification resin, there may be mentioned a method comprising: an aluminum halide (A) selected from a halogenated hydrocarbon bonded to a carbon atom of a third order by a halogen atom (B1) And a halogenated hydrocarbon (B) grouped with a halogenated hydrocarbon (B2) having a halogen atom bonded to a carbon atom adjacent to the carbon-carbon unsaturated bond is combined and used as a polymerization catalyst, and then contains 1 , 3-pentadiene 20% by mass to 70% by mass, carbon number 4-6 alicyclic monoolefin 10% by mass to 35% by mass, carbon number 4-8, acyclic monoolefin 3% by mass to 30 mass The polymerization step of polymerizing the monomer mixture A of %, alicyclic diene 0% by mass to 10% by mass, and aromatic monoolefin 0% by mass to 40% by mass.

Specific examples of the aluminum halide (A) include aluminum chloride (AlCl ₃ ) and aluminum bromide (AlBr ₃ ). Among them, aluminum chloride is suitably used from the viewpoint of versatility and the like.

The amount of use of the aluminum halide (A) is not particularly limited, and is preferably in the range of 0.05 parts by mass to 10 parts by mass, more preferably 0.1 part by mass, per 100 parts by mass of the polymerizable component (monomer mixture A). Within 5 parts by mass.

By using the halogenated hydrocarbon (B) in combination with the halogenated hydrocarbon (A), the activity of the polymerization catalyst is extremely good.

Specific examples of the halogenated hydrocarbon (B1) in which a halogen atom is bonded to a tertiary carbon atom include a third butyl chloride, a third butyl bromide, 2-chloro-2-methylbutane, and the third. Phenylmethyl chloride. Among them, based on activity From the viewpoint of excellent balance of ease of handling, it is particularly suitable to use a third butyl chloride.

Examples of the unsaturated bond of the halogenated hydrocarbon (B2) in which a halogen atom is bonded to a carbon atom adjacent to a carbon-carbon unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond, and an aromatic ring or the like. Carbon-carbon conjugated double bond. Specific examples of such a compound include benzyl chloride, benzyl bromide, (1-chloroethyl)benzene, allyl chloride, 3-chloro-1-propene, 3-chloro-1-butene Alkene, 3-chloro-1-butyne, cinnamic acid chloride. Among them, a benzyl chloride is suitably used from the viewpoint of excellent balance between activity and ease of handling. In addition, one type of the halogenated hydrocarbons (B) may be used, or two or more types may be used in combination.

The halogenated hydrocarbon (B) is used in an amount of preferably from 0.05 to 50, more preferably from 0.1 to 10, based on the molar ratio of the aluminum halide (A).

When the polymerization reaction is carried out, the order of adding the monomer mixture and the respective components of the polymerization catalyst to the polymerization reactor is not particularly limited, and may be added in any order, and the polymerization reaction is well controlled, and further precise From the viewpoint of controlling the weight average molecular weight, it is preferred to add a monomer mixture and a part of the polymerization catalyst to the polymerization reactor, and after the polymerization reaction is started, the remainder of the polymerization catalyst is added to the polymerization reactor.

When the resin is modified prior to the modification, first, it is preferred to mix the aluminum halide (A) with the alicyclic terpene. By contacting the aluminum halide (A) with the alicyclic terpene, it is possible to prevent gel formation and to obtain a pre-modification resin which has been precisely controlled such as a weight average molecular weight.

The amount of the alicyclic monoolefin mixed with the aluminum halide (A) is preferably at least 5 times (mass ratio) of the amount of the aluminum halide (A). Alicyclic monoolefin When the amount is too small, there is a problem that the gel formation prevention effect is insufficient. The quality of the alicyclic monoolefin and the aluminum halide (A) is preferably from 5:1 to 120:1, more preferably from 10:1 to 100:1, and still preferably from 15:1 to 80:1. When the alicyclic monoolefin is excessively used in this ratio, the catalytic activity is lowered and the polymerization is not sufficiently carried out.

When the aluminum halide (A) and the alicyclic monoolefin are mixed, the order of the input is not particularly limited, and the aluminum halide (A) may be introduced into the alicyclic monoolefin, or the alicyclic monomer may be used. The olefin is introduced into the aluminum halide (A). Mixing is usually accompanied by heat, so a suitable diluent can also be used. As a diluent, the solvent mentioned later can be used.

The above is carried out, and after the mixture M of the aluminum halide (A) and the alicyclic monoolefin is prepared, it is preferred to mix at least the mixture a and the mixture M containing the 1,3-pentadiene and the acyclic monoolefin. Mix it. An alicyclic diene may also be contained in the mixture a.

The preparation method of the mixture a is not particularly limited, and a single compound may be separately mixed to obtain the target mixture a, and for example, a mixture containing the target monomer derived from a petroleum brain decomposition product or the like may be used. The target mixture a is obtained. For example, in order to incorporate 1,3-pentadiene or the like into the mixture a, a C5 fraction obtained by extracting isoprene and cyclopentadiene (including a multimer thereof) can be suitably used.

It is preferred to further mix the halogenated hydrocarbon (B) together with the mixture a and the mixture M. The order in which these three items are put is not particularly limited.

From the viewpoint of further controlling the polymerization reaction, it is preferred to add a solvent to the polymerization reaction system to carry out the polymerization reaction. If the type of solvent is such that it does not interfere with the polymerization reaction, it will not It is particularly limited to be suitable for saturated aliphatic hydrocarbons or aromatic hydrocarbons. The saturated aliphatic hydrocarbon to be used as the solvent may, for example, be n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane or 3-methyl. Hexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, a chain-like saturated aliphatic hydrocarbon having 5 to 10 carbon atoms such as 2,2,3-trimethylbutane or 2,2,4-trimethylpentane; cyclopentane, cyclohexane, cycloheptane, and ring A cyclic saturated aliphatic hydrocarbon having a carbon number of 5 to 10 such as octane. Examples of the aromatic hydrocarbon used as the solvent include aromatic hydrocarbons having a carbon number of 6 to 10 such as benzene, toluene or xylene. The solvent system may be used singly or in combination of two or more. The amount of the solvent to be used is not particularly limited, and is preferably in the range of 10 parts by mass to 1,000 parts by mass, more preferably 50 parts by mass to 500 parts by mass, per 100 parts by mass of the polymerizable component (monomer mixture A). Within the scope. Further, for example, a mixture of an addition polymerizable component and a non-addition polymerizable component such as a mixture of cyclopentane and cyclopentene derived from a C5 fraction is added to a polymerization reaction system, and an addition polymerizable component can be used. The component of the monomer mixture is used in the form of a component, and the non-addition polymerizable component may also be used in the form of a solvent.

The polymerization and temperature at the time of carrying out the polymerization reaction are not particularly limited, and are preferably in the range of from -20 ° C to 100 ° C, preferably in the range of from 0 ° C to 75 ° C. When the polymerization temperature is too low, the polymerization activity may be lowered and the productivity may be poor. When the polymerization temperature is too high, the controllability of the weight average molecular weight of the resin before the modification may be poor. The pressure at which the polymerization is carried out may be under atmospheric pressure or under pressure. The polymerization time can be appropriately selected, and it usually takes from 10 minutes to 12 hours, preferably from 30 minutes to 6 minutes. The range of hours is chosen.

The polymerization reaction can be stopped by adding a polymerization stopper such as methanol, an aqueous sodium hydroxide solution or an aqueous ammonia solution to the polymerization reaction system when the desired polymerization conversion ratio is obtained. Further, a polymerization stopper may be added, and the insoluble catalyst residue may be removed by filtration or the like for the solvent generated when the polymerization catalyst is deactivated. After the polymerization reaction is stopped, the unreacted monomer and the solvent are removed, and the low molecular weight oligomer component is further removed by steam distillation or the like, and cooled, whereby a solid pre-modification resin can be obtained.

2. Organic decane compounds

The above organodecane compound is represented by the following formula (1).

X ₃ Si-RF-[R-Si-X ₃ ] _p (1)

(In the formula (1), each of the X systems is independently a helium atom-bonding functional group, and each of the R systems is independently, and is a divalently substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, and F is 1 or more. The organic functional group of the valence, when F is 1 valence, p is 0, and when F is multivalent, p is at least 1).

The X system in the formula (1) may be a ruthenium atom-bonding functional group, and may be, for example, a hydroxyl group or a group represented by R ¹ -O-. Here, the so-called ruthenium atom-bonding functional group means a functional group bonded to a ruthenium atom.

Further, R ¹ is preferably an alkyl group, an alkoxyalkyl group, an aryl group or an aralkyl group having 20 carbon atoms (preferably 10 carbon atoms, particularly preferably 1 to 5 carbon atoms). Or a cycloalkyl group.

In the present invention, the above X is preferably an alkoxyalkyl group from the viewpoint of dispersibility of cerium oxide. The decane-modified hydrocarbon resin of the present invention can impart an elastomer composition for a tire excellent in wet grip performance.

R in the formula (1) may be a divalently substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, and preferably a carbon atom of 10 or more preferably 1 to 5 carbon atoms. base. Since R is a hydrocarbon group as described above, the decane-modified hydrocarbon resin of the present invention can impart an elastomer composition for a tire excellent in wet grip performance.

The F in the formula (1) is a monovalent or polyvalent organic functional group which is a direct or indirect bonding site with the pre-modification resin.

As such an organic functional group F, when p is 0, for example, it may be an amine group, a guanamine group, a hydroxyl group, an alkoxy group (usually 20 carbon atoms), a halogen group, a thio group, a hydrazine group. , carboxyl, fluorenyl (usually 20 carbon atoms), vinyl, allyl, styryl, ureido, epoxy, isocyanate, decyl, epoxypropoxy, and propylene The base chosen.

The organofunctional group F in the formula (1) may be, for example, a divalent polysulfide group of 2 to 20 sulfur atoms when p is 1.

In the present invention, it is preferred that the organic functional group F is a vinyl group, a thiol group, a polysulfide group or an amine group. Since the above-mentioned organofunctional group F can easily reform the decane of the pre-modification resin.

As a specific example of such an organic decane compound, for example, a bifunctional organodecane crosslinking agent as disclosed in JP-A-2015-4074 can be used.

In the present invention, the organodecane compound is preferably 3-aminopropyltriethoxydecane, bis[3-(triethoxyindolyl)propyl]tetrasulfide or the like. The above decane compound is excellent in reactivity with the pre-modification resin.

Further, the organic decane compound 矽 may be contained in only one type, or may be a mixture of two or more types.

The content of the organodecane compound in the decane-modified hydrocarbon resin of the present invention, that is, the content of the bonded organic decane compound relative to 100 parts by mass of the hydrocarbon resin belonging to the pre-modified resin is 0.1 part by mass. It is preferably in the range of from 10 parts by mass, preferably from 0.1 part by mass to 9 parts by mass, more preferably from 0.1 part by mass to 8 parts by mass, and preferably from 0.1 part by mass to 7 parts by mass. Nite Jia. When the above-mentioned content is within the above range, the decane-modified hydrocarbon resin of the present invention can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The decane upgrading method as the pre-modification resin using the above organodecane compound is bonded to the pre-modification resin by the organofunctional group F of the organodecane compound and can have a decane structure (-R-SiX _{3 )} The method of modifying the hydrocarbon resin can be.

Such decane upgrading methods can employ suitable well-known methods.

Specifically, as the decane reforming reaction, a pre-modification resin, an organic decane compound, and a peroxide initiator may be mixed to form a free radical before the reforming resin by using a peroxide initiator. A method of reacting this with an organic functional group F of an organodecane compound; a method of mixing an organodecane compound with a pre-modification resin having an active terminal;

Further, in the case of such a decane reforming reaction, when the organofunctional group F is a polysulfide group, for example, it may be partially cleaved as a polysulfide, and the sulfur atom at the end of the cleavage is bonded before the modification. Resin.

In the above decane upgrading method, the amount of the organic decane compound added to the resin before the reforming is as desired for bonding. The amount of the organic decane compound may be, for example, an amount of the same amount or more as the content of the organic decane compound in the decane-modified hydrocarbon resin.

The reaction conditions of the above-described decane upgrading method using free radicals may be such that the desired amount of the organodecane compound is bonded to the pre-modification resin, and the type of the resin before the modification, the organic decane compound may be used. The type is appropriately set, for example, at a reaction temperature of 0 ° C to 200 ° C and a reaction time of 5 minutes to 20 hours.

Further, the above decane reforming method can be carried out, for example, in an organic solvent.

As such an organic solvent, it can be the same as the solvent which can be used for the polymerization reaction of the pre-modification resin contained in the above-mentioned "1. Hydrocarbon Resin". The above decane upgrading method may be, for example, a method of modifying decane in a solvent obtained by pre-modification of a resin and a solvent to be used.

As the peroxide initiator, for example, a desired amount of the organodecane compound may be bonded to the pre-modification resin. For example, an inorganic peroxide such as sodium persulfate or diisopropylbenzene can be used. A known peroxide initiator such as an organic peroxide such as a hydroperoxide.

Further, as such an inorganic peroxide, an organic peroxide or the like, for example, those disclosed in JP-A-2004-285230 and the like can be used.

The peroxide initiator is used in an amount such that the desired amount of the organodecane compound is bonded to the pre-modification resin, and can be appropriately set depending on the amount of the organodecane compound added or the like.

The decane upgrading method may be a method of bonding an organodecane compound to a pre-modification resin via a known decane coupling agent (except for those corresponding to the above organodecane compound) as needed. In addition The method of bonding the decane coupling agent to the pre-modification resin may be the same as the above decane upgrading method.

For the decane coupling agent, for example, a bifunctional decane coupling agent having a reaction functional group capable of bonding an organic functional group F which is a vinyl group or an organic decane compound can be used.

The functional group for the above reaction can be appropriately set depending on the organic functional group F of the organodecane compound.

For example, when the organic functional group F is an amine group or the like, a hydroxyl group, a carboxyl group, an amine group, a urea group, a glycidoxy group, a halogen group, a sulfonic acid group or the like can be used as the functional group for the reaction. Further, when the hydroxyl group or the like is exemplified as the functional group for the reaction of the organic functional group F, an amine group or the like may be used as the functional group for the reaction.

Further, the bifunctional decane coupling agent having such a vinyl group and a reactive functional group can be appropriately selected from known decane coupling agents.

In addition, the blending amount of the decane coupling agent used as a spacer between the organic decane compound and the pre-modification resin can be appropriately set as long as it does not impair the appearance of the effect of the present invention.

As a method of bonding the pre-modification resin to which the decane coupling agent is bonded, and the organodecane compound, for example, a pre-modification resin to which a decane coupling agent is bonded and an organic decane compound are mixed and heated. The method of processing.

The heat treatment conditions may be, for example, 5 minutes to 20 hours in the range of 50 ° C to 300 ° C.

In the above heat treatment, a diluent, a gel inhibitor, a reaction accelerator, and the like may be present as needed.

As such a diluent, it may be the same as the solvent used for the polymerization reaction of the pre-modification resin contained in the above-mentioned "1. Hydrocarbon resin". The heat treatment may be, for example, a method carried out in a solvent used in the polymerization of the resin before the reforming.

Further, the organofunctional group F in the organodecane compound is an amine group, a decylamino group, a hydroxyl group, a carboxyl group, a thiol group, a vinyl group, an allyl group, a styryl group, a ureido group, a decyl group, an acryl group, a halogen group. In the above, the decane reforming method may be a method in which an organic sulfonate compound is reacted with an acidic group such as a carboxyl group contained in the pre-modified resin to bond the organodecane compound to the pre-modification resin.

With respect to the above acidic group, the acidic group introduced in the pre-modification resin can be used by using a polymerizable component (monomer mixture A) containing a monomer having an acidic group, and the pre-modification resin can also be used. Acidic group introduced by acid modification.

Here, as a method of acid-modifying the resin before the modification, a known method can be employed. For example, when a carboxyl group is introduced as an acidic group, the pre-modification resin and the unsaturated carboxylic acid are mixed and heated. The method of processing.

Examples of the unsaturated carboxylic acid to be used for the introduction of the carboxyl group include a conjugated diene such as maleic acid and a Diels-Alder adduct of an α,β-unsaturated carboxylic acid having 8 or less carbon atoms.

Moreover, the blending amount of the acid modifier such as an unsaturated carboxylic acid introduced by acid-modifying the pre-modification resin can be appropriately set as long as it does not impair the effects of the present invention.

As the reaction condition of the above acid reforming reaction, for example, it can be set as a temperature 5 minutes to 20 hours in the range of 50 ° C ~ 300 ° C.

The acid modification reaction may be carried out by a diluent, a gel inhibitor, a reaction accelerator or the like as needed.

Moreover, as a reaction which bonds an acidic group and an organic decane compound, the method of mixing the pre-modification resin and the organic decane compound after the modification of the resin or acid after the modification, and heat-processing is mentioned. The heat treatment method may be, for example, the same as the heat treatment method in which the pre-modification resin and the organodecane compound to which the above-described decane coupling agent is bonded are bonded.

3. Hydrocarbon resin modified by decane

The weight average molecular weight (Mw) of the decane-modified hydrocarbon resin is not particularly limited as long as it is in the range of 1,000 to 8,000, and preferably in the range of 1,200 to 6,000, particularly preferably in the range of 1,400 to 4,500. Inside. Since the weight average molecular weight (Mw) is within the above range, the hydrocarbon resin modified with decane can be excellent in compatibility with an elastomer. Further, as a result, the hydrocarbon resin modified with decane can easily reduce the loss tangent tan δ at 60 ° C for the crosslinked product of the elastomer composition, and is excellent in rolling resistance.

Further, since the weight average molecular weight (Mw) is within the above range, the hydrocarbon resin modified with decane can easily increase the loss tangent tan δ at 0 ° C, and it is excellent in rolling resistance.

The Z-average molecular weight (Mz) of the above-mentioned decane-modified hydrocarbon resin is not particularly limited as long as it is in the range of 2,000 to 25,000, and particularly preferably in the range of 3,000 to 20,000, particularly preferably 4,000 to 15,000. Within the scope. Because by Z average molecular weight (Mz) in the above range In the periphery, the hydrocarbon resin modified with decane can be excellent in compatibility with an elastomer. Further, as a result, the hydrocarbon resin modified with decane can easily reduce the loss tangent tan δ at 60 ° C for the crosslinked product of the elastomer composition, and is excellent in rolling resistance.

Further, in the present invention, the weight average molecular weight (Mw) and the Z average molecular weight (Mz) of the decane-modified hydrocarbon resin are determined by a value in terms of polystyrene measured by high-speed liquid chromatography.

More specifically, the measurement of the weight average molecular weight and the Z average molecular weight can be performed by using "HLC-8320GPC" manufactured by TOSOH Co., Ltd. as a measuring device, and the column system is connected with "TSKgel Super Multipore HZ" manufactured by three TOSOH companies. Tetrahydrofuran was used as a solvent and measured at a flow rate of 1.0 mL/min at 40 °C.

The ratio of the Z average molecular weight to the weight average molecular weight (Mz/Mw) of the above decane-modified hydrocarbon resin is not particularly limited as long as it is in the range of 1.0 to 4.5, and preferably, it is in the range of 1.0 to 4.0. Within the range of 1.0 to 3.5. The hydrocarbon resin modified with decane can be excellent in compatibility with an elastomer by the above-mentioned ratio within the above range. Further, as a result, the hydrocarbon resin modified with decane can easily reduce the loss tangent tan δ at 60 ° C for the crosslinked product of the elastomer composition, and is excellent in grip performance when wet.

The softening point of the above-mentioned decane-modified hydrocarbon resin is not particularly limited as long as it is in the range of 80 ° C to 110 ° C, and preferably in the range of 85 ° C to 110 ° C, particularly preferably 90 ° C to 110 ° C. Within the scope. Since the above-mentioned softening point is within the above range, the hydrocarbon resin modified with decane can be excellent in compatibility with an elastomer. Again, the result is modified by decane The hydrocarbon resin can easily reduce the loss tangent tan δ at 60 ° C for the crosslinked product of the elastomer composition, so that it is excellent in rolling resistance.

Further, since the softening point is in the above range, the hydrocarbon resin modified with decane can easily increase the loss tangent tan δ at 0 ° C, and it is excellent in grip performance when wet.

Further, the softening point of the present invention is, for example, a modified hydrocarbon resin, a value measured in accordance with JIS K6863.

The glass transition temperature of the decane-modified hydrocarbon resin may be excellent in compatibility with an elastomer, and may be, for example, in the range of 30 ° C to 60 ° C, and preferably 35 ° C to 60 ° C. Within the range of °C, it is particularly preferably in the range of 40 ° C to 60 ° C. Since the glass transition temperature is within the above range, the hydrocarbon resin modified with decane can be excellent in compatibility with the elastomer. Further, as a result, for example, the loss tangent tan δ of the elastomer composition at 60 ° C can be easily reduced, so that the workability is excellent and the rolling resistance is excellent, and the loss tangent tan δ at 0 ° C can be easily improved, so that the wet grip performance is obtained. Excellent.

From this, it is understood that the glass transition temperature is within the above range, and it is possible to impart an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

Further, the glass transition temperature of the present invention can be measured, for example, by differential scanning calorimetry (DSC) at a temperature increase rate of 10 ° C /min. Further, as the measuring device, for example, Pyrisl DSC (manufactured by Perkinelmer Co., Ltd.) can be used.

The decane-modified hydrocarbon resin of the present invention can be used, for example, in an elastomer composition for various purposes as a mixture with an elastomer. Used as a hydrocarbon resin.

In the present invention, as described above, the decane-modified hydrocarbon resin can give an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

In this way, the above-mentioned decane-modified hydrocarbon resin is used in a flexible manner, and can be suitably used as a hydrocarbon resin to be used in an elastomer composition for a tire and mixed with an elastomer.

As a method for producing the above-described decane-modified hydrocarbon resin, a method of modifying the decane by using 0.1 part by mass to 10 parts by mass of the organodecane compound represented by the above formula (1) to be a pre-modification resin may be employed. 100 parts by mass of the hydrocarbon resin was modified.

In addition, the method of modifying the above-described organic decane compound, that is, the decane reforming method or the like, may be the same as those described in the above-mentioned "2. Organic decane compound", and thus the description thereof will be omitted.

B. Elastomer composition for tires

Next, the elastomer composition for a tire of the present invention will be described.

The elastomer composition for a tire of the present invention is characterized by comprising at least one elastomer and the above-described decane-modified hydrocarbon resin.

According to the present invention, by using the above-described decane-modified hydrocarbon resin, it is possible to produce a tire excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The elastomer composition for a tire of the present invention has an elastomer, a filler, and a decane-modified hydrocarbon resin.

Hereinafter, each component of the elastomer composition for a tire of the present invention will be described in detail.

1. Hydroxyl resin modified by decane

The content of the decane-modified hydrocarbon resin may be any elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The content is, for example, in the range of 0.1 part by mass to 50 parts by mass based on 100 parts by mass of the elastomer, and particularly preferably in the range of 1 part by mass to 30 parts by mass, particularly preferably 1.5 parts by mass. ~20 parts by mass. When the content is within the above range, the elastomer composition for a tire can be excellent in workability and excellent in balance between rolling resistance and wet grip performance.

Further, the above-mentioned decane-modified hydrocarbon resin may be the same as those described in the above-mentioned "A. Hydrocarbyl-modified hydrocarbon resin", and thus the description thereof will be omitted.

2. Elastomer

As the above elastomer, a known elastomer used for the elastomer composition for a tire can be used.

Examples of such an elastomer include natural rubber, polyisoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, solution-polymerized styrene-butadiene copolymer rubber, and polybutadiene rubber (also It is a high-cis-BR, a low-cis BR, or a polybutadiene rubber containing a crystalline fiber composed of a 1,2-polybutadiene polymer, a styrene-isoprene copolymer rubber, Butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylonitrile-styrene-butadiene copolymer rubber, and the like.

In addition, the above elastic system may be at least one type, and may be only a package. Including one type, it is also possible to mix two or more types of users.

3. Filler

As the filler, those generally used for the elastomer composition for tires can be used, and examples thereof include carbon black, clay, diatomaceous earth, cerium oxide, talc, barium sulfate, calcium carbonate, magnesium carbonate, and metal oxide. , mica, graphite, aluminum hydroxide, various metal powders, wood powder, glass powder, ceramic powder, etc., as well as inorganic hollow fillers such as glass balloons and cerium oxide balloons; from polystyrene, poly(difluoroethylene), An organic hollow filler composed of a poly(difluoroethylene) copolymer or the like.

Among the above-mentioned fillers, for example, cerium oxide, carbon black, or the like can be used as described in JP-A-2016-30795.

In the present invention, the filler is preferably cerium oxide. Since the filler is made of cerium oxide, the elastomer composition for a tire can be excellent in wet grip performance.

In addition, the filler may be contained in at least one type, and may be used alone or in combination of two or more.

The content of the filler may be an elastomer composition for a tire which is excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The content is, for example, in the range of 30 parts by mass to 250 parts by mass based on 100 parts by mass of the elastomer, and preferably in the range of 30 parts by mass to 200 parts by mass, particularly preferably 40 parts by mass. Within the range of ~150 parts by mass, particularly preferably in the range of 50 parts by mass to 130 parts by mass. When the content is within the above range, the elastomer composition for a tire can be excellent in workability and wet grip performance.

4. Elastomer composition for tires

The elastomer composition for a tire of the present invention has an elastomer, a filler, and a decane-modified hydrocarbon resin, and may contain other components as needed.

As other components, for example, a mixture of a decane coupling agent, a crosslinking agent, a crosslinking accelerator, a crosslinking activation agent, an antioxidant, an active agent, a process oil, a plasticizer, a slip agent, and an adhesive may be blended according to respective requirements. A blending agent or the like is added.

In addition, as such other components and the content thereof, for example, the same as those described in JP-A-2016-30795 can be used.

The method for producing an elastomer composition for a tire according to the present invention may be a method in which the respective components are kneaded by a usual method. For example, after the components of the component which is unstable to heat, such as a crosslinking agent and a crosslinking accelerator, are removed, the elastomer may be kneaded. A component such as a crosslinking agent or a crosslinking accelerator is mixed with the heat-labile component and the kneaded product to obtain a target composition. The mixing temperature of the component and the elastomer which removes the component which is unstable to heat is preferably in the range of 80 ° C to 200 ° C, more preferably in the range of 120 ° C to 180 ° C, and the mixing time is 30 seconds to 30 seconds. minute. Further, the mixing of the kneaded material and the component which is unstable to heat is usually carried out after cooling to 100 ° C or lower (preferably 80 ° C or lower).

As a crosslinking method of the elastomer composition for a tire of the present invention as a crosslinker for an elastomer for a tire, a known crosslinking method can be employed, for example, by a molding machine corresponding to a desired shape, for example, an extruder. A method in which a molding machine, a compressor, a drum, and the like are injection molded, heated, and subjected to a crosslinking reaction to fix a shape by a crosslinked product. In this case, the crosslinking may be carried out after the preforming, or the crosslinking may be carried out while molding. The forming temperature is usually in the range of 10 ° C ~ 200 ° C Within the circumference, it is preferably in the range of 25 ° C to 120 ° C. The crosslinking temperature is usually in the range of 100 ° C to 200 ° C, preferably in the range of 130 ° C to 190 ° C, particularly preferably in the range of 130 ° C to 190 ° C, and the crosslinking time is usually in the range of 1 minute to 24 hours. Preferably, it is in the range of 2 minutes to 12 hours, and particularly preferably in the range of 3 minutes to 6 hours.

Further, depending on the shape and size of the crosslinked body of the elastomer for tires, even if the surface is crosslinked and the inside is not sufficiently crosslinked, the cross-linking method may be further heated to perform secondary crosslinking.

As the heating method, a general method used for crosslinking of the elastomer composition such as press heating, steam heating, furnace heating, or hot air heating can be appropriately selected.

Since the elastomer composition for a tire of the present invention can provide a tire excellent in balance between rolling resistance and wet grip performance, it is excellent in low heat build-up and wet grip performance. Then, the elastomer composition of the present invention can flexibly utilize such characteristics and is suitable for use in materials such as tire spacing track, base track, automobile frame, side wall, ball portion, and the like, wherein Among the various types of tires such as the four seasons general tires, high-performance tires, and tireless tires, they can be suitably used in various parts of the tire such as the wheelbase, the automobile frame, the side wall, and the ball portion, and are particularly suitable for low heat generation. Use as a track for low-burning tires.

The present invention is not limited to the above embodiment. The above-described embodiments are exemplified as long as they have substantially the same configuration as the technical idea contained in the patent application scope of the present invention, and are included in the technical scope of the present invention in order to achieve the same effects.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. In addition, the parts and % in each example are based on the quality without being particularly limited.

For various measurements, the following methods are performed.

[Weight average molecular weight, Z average molecular weight, and molecular weight distribution]

The decane-modified hydrocarbon resin to be a sample was subjected to gel permeation chromatography to obtain a weight average molecular weight (Mw) and a Z average molecular weight (Mz) in a standard styrene-converted value, and the molecular weight distribution was Mz/Mw. More than to show. In addition, the gel permeation chromatography was performed using "HLC-8320GPC" manufactured by TOSOH Co., Ltd. as a measuring device, and the column was connected with three "TSKgel Super Multipore HZ" manufactured by TOSOH Co., Ltd., and tetrahydrofuran was used as a solvent. The measurement was carried out at a flow rate of ° C and 1.0 mL/min.

[Softening point (°C)]

The decane-modified hydrocarbon resin of the sample was measured in accordance with JIS K6863.

[Muni Viscosity (ML1+4)]

The elastomer composition of the sample was measured under the following conditions in accordance with JIS K6300-1:2001.

‧ Test temperature: 100 ° C

‧Type of drum: L shape

‧Using test machine: Shimadzu Manufacturing Co., Ltd. System Shimadun Viscometer SMV-300J

[tensile strength (MPa) and elongation (%)]

With respect to the test piece of the elastomer crosslinked product of the sample, tensile strength (MPa) and elongation were measured in accordance with JIS K6251:2010 under the following conditions.

‧Test piece production method: After making the sheet by pressing and adding sulfur, punching is performed

‧ test piece shape: dumbbell shape 3

‧The test piece takes the direction: parallel to the texture

‧Number of trials: 3

‧Measurement temperature: 23 ° C

‧ Test speed: 500mm/min

‧Use test machine: TENSOMETER 10k made by ALPHA TECHNOLOGIES

‧Testing machine capacity: dynamometer type 1kN

[loss tangent tan δ]

With respect to the test piece of the elastomer crosslinked product of the sample, the loss tangent tan δ at 0 ° C and 60 ° C under dynamic strain of 0.5% and 10 Hz was measured in accordance with JIS K7244-4 under the following measurement conditions. This characteristic is expressed by an index of a reference sample (Comparative Example 1 described later) of 100.

Further, the higher the loss tangent tan δ at 0 ° C, the better the wet grip performance, and the lower the tangent tan δ at 60 ° C, the more excellent the rolling resistance.

Measurement item: Dynamic storage elastic coefficient E’

: Dynamic loss elastic coefficient E"

: loss tangent tan δ

‧ Sample preparation method: perforation processing from sheet

‧ Test piece shape: length 50mm × width 2mm × thickness 2mm

‧Number of trials: 1

‧ Distance between clamps: 20mm

[Example 1]

To the polymerization reactor, a mixture of 47.3 parts of cyclopentane and 28.3 parts of cyclopentene was added to the polymerization reactor, and after raising the temperature to 70 ° C, 0.75 parts of aluminum chloride (mixture M ₁ ) was added.

Next, while maintaining the temperature (70 ° C) for 60 minutes, 63.6 parts of 1,3-pentadiene, 6.2 parts of isoprene, 0.1 part of dicyclopentadiene, 0.3 parts of C4 to C6 unsaturated hydrocarbon, and C4 to C6. The mixture a ₁ composed of 5.7 parts of a saturated hydrocarbon was continuously added to the polymerization reactor containing the mixture M ₁ while being polymerized. Thereafter, an aqueous sodium hydroxide solution was added to the polymerization reactor to terminate the polymerization reaction. Further, the types and amounts of the components in the polymerization reactor at the time of the polymerization reaction are shown in Table 1. After the precipitate formed by the polymerization stop was removed by filtration, the obtained polymer solution was placed in a distillation pot and heated under a nitrogen atmosphere to remove the polymerization solvent and the unreacted monomer. Next, the low molecular weight oligomer component is distilled off while blowing saturated steam at 240 ° C or higher.

To the 100 parts of the resin in a molten state, pentaerythritol 肆[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Corporation, trade name: IRGANOX1010) was added as an antioxidant. 0.2 parts, secondly, 2.0 parts of maleic anhydride was added, and after the addition reaction was carried out at 230 ° C for 1 hour, 1.5 parts of 3-aminopropyltriethoxydecane as an organic decane compound was added, and the mixture was added at 230 ° C. The addition reaction was carried out for 1 hour. Thereafter, from The molten resin was taken out from the distillation pot and allowed to cool to room temperature to obtain a decane-modified hydrocarbon resin of Example 1. The weight average molecular weight, the Z average molecular weight, the molecular weight distribution, and the softening point of the obtained decane-modified hydrocarbon resin of Example 1 were measured. The results of these measurements are summarized in Table 1 below.

In addition, the values of the organodecane compound (parts) and the pre-modification resin (100 parts) in Table 1 were calculated by using maleic anhydride used for acid modification as a part of the raw material of the pre-modification resin. The amount (parts) of the organic decane compound added to the total of 100 parts of the monomer mixture constituting the pre-modification resin and the maleic anhydride contained in Table 1 is shown.

[Embodiment 2]

The type and amount of the components to be added to the polymerization reactor and the polymerization temperature were changed as shown in Table 1, except that the hydrocarbon resin was obtained in the same manner as in Example 1. Further, diisobutylene and an aromatic monoolefin are mixed with 1,3-pentadiene and supplied to the polymerization.

Further, with respect to 100 parts of the above-mentioned resin in a molten state, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by BASF Corporation) was added as an antioxidant. Name: IRGANOX 1010) 0.2 part of 3.0 parts of bis[3-(triethoxyindenyl)propyl]tetrasulfide as an organic decane compound, and an addition reaction was carried out at 230 ° C for 1 hour. Thereafter, the molten resin was taken out from the distillation pot and allowed to cool to room temperature to obtain a decane-modified hydrocarbon resin of Example 2. The weight average molecular weight, the Z average molecular weight, the molecular weight distribution, and the softening point of the obtained decane-modified hydrocarbon resin of Example 2 were measured. The results of these measurements are summarized in Table 1 below.

In addition, the values of the organodecane compound (part)/pre-modification resin (100 parts) in Table 1 represent the single raw materials of the pre-modification resin as shown in Table 1. The amount of the organic decane compound added in portions (parts) of the mixture of the mixture.

[Examples 3 to 4, Comparative Examples 1 to 4]

The types and amounts of the components to be added to the polymerization reactor and the polymerization temperature were changed as shown in Table 1, except that the same procedures as in Example 1 or 2 were carried out, and Examples 3 to 4 and Comparative Examples were respectively obtained. 1~4 of a decane-modified hydrocarbon resin. Specifically, in Example 3 and Comparative Example 3, in the same manner as in Example 1, after the pre-modification resin was acid-modified, a decane-modified hydrocarbon resin was obtained. Further, in Example 4 and Comparative Example 4, the organodecane compound was directly bonded to the pre-modification resin in the same manner as in Example 2 to produce a decane-modified hydrocarbon resin. Further, in Comparative Example 1 and Comparative Example 2, the decane reforming via the organodecane compound was not carried out to obtain a hydrocarbon resin modified with decane.

Further, the diisobutylene, the aromatic monoolefin, and the toluene which are not described in the first or second embodiment are mixed with 1,3-pentadiene and supplied to the polymerization.

[Manufacture and Evaluation of Elastomer Compositions and Elastomer Crosslinks]

In a Bamburi mixer, 100 parts of solution-polymerized styrene-butadiene rubber (S-SBR) was mixed for 30 seconds, and then cerium oxide (manufactured by Rhodia Co., Ltd., "Zeosil 1115MP") 53.0 was added. And decane coupling agent: bis [3-(triethoxyindenyl) propyl] tetrasulfide (manufactured by Degussa Co., Ltd., trade name "Si69") 7.0 parts and modified by decane obtained in Example 1. 5 parts of a hydrocarbon resin, after kneading for 90 seconds, 32.0 parts of cerium oxide (trade name "Zeosil 1115MP" by Rhodia Co., Ltd.), 3.0 parts of zinc oxide, 2.0 parts of stearic acid, and an anti-aging agent: N-phenyl- N'-(1,3-dimethylbutyl)-p-phenylenediamine (manufactured by Ouchi Emerging Co., Ltd., trade name " 2.0 parts of Nocrac 6C" was further kneaded for 90 seconds, and then 25 parts of process oil (manufactured by Shin-Nippon Oil Co., Ltd., trade name "Aromax T-DAE") was put.

Thereafter, the mixture was kneaded at a temperature of 90 ° C, and kneaded at 145 ° C to 155 ° C for 60 seconds or more, and then the kneaded material was taken out from the mixer.

After the obtained kneaded material was cooled to room temperature, it was again placed in a Bamburi mixer at a temperature of 90 ° C and kneaded for 2 minutes (2 kneading), and then the kneaded material was taken out from the mixer. The temperature of the kneaded mixture at the end of the kneading was 145 °C.

Next, using the two rolls at 50 ° C, 2.0 parts of sulfur and a vulcanization accelerator were added to the obtained kneaded material: N-cyclohexyl-2-benzothiazolyl decyl decylamine (CBS trade name "Nocceler CZ-G" 1.9 parts of 胍 大 大 DP DP DP DP DP DP DP DP DP DP DP DP DP DP DP DP ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Body composition.

The elastomer composition was subjected to compression crosslinking at a pressing pressure of about 8 MPa and a pressing temperature of 160 ° C for 40 minutes, and then further matured in a constant temperature room at 23 ° C for one night to prepare 150 mm × 150 mm × thickness 2 mm. Test piece of elastomer crosslinker.

With respect to the elastomer composition and the elastomer crosslinked product obtained by using the obtained decane-modified hydrocarbon resin of Example 1, the Muss viscosity of the elastomer composition and the tensile strength of the elastomer crosslinked product were measured. (MPa), elongation (%), and loss tangent tan δ. The results are shown in Table 1.

The obtained decane-modified hydrocarbon resins of Examples 2 to 4 and Comparative Examples 1 to 4 were each subjected to the same operation to obtain an elastomer composition and The elastomer crosslinked product was measured for the Muss viscosity of the elastomer composition, the tensile strength (MPa) of the elastomer crosslinked product, the elongation (%), and the loss tangent tan δ. The results are shown in Table 1.

In addition, the kneading conditions of one kneading, two kneading, and a vulcanizing agent kneading are as follows.

(1 mixing and 2 mixing exercises)

‧Testing machine: LABO PLASTO MILL Bamburi Mixer B-600 made by Toyo Seiki Co., Ltd.

‧ Filling rate: 70~75% by volume

‧Roller rotation number: 50rpm

‧ Test start set temperature: 90 ° C

(mixing conditions of vulcanizing agent mixing)

‧Testing machine: Ikeda Machinery Industry Co., Ltd. Electric heating type high temperature roller machine

‧Drum size: 6 ×16

‧ Front drum rotation number: 24rpm

‧ Front and rear drum rotation ratio: 1:1.22

‧Roller temperature: 50 °C ± 5 °C

‧Number of crossings: 2 times each

‧ Round through width: drum spacing is about 0.8mm

‧ Round number of passes: 5 times

It can be confirmed from Table 1 that, in the case of the embodiment, the loss at 0 ° C The tangent tan δ is high, and the loss tangent tan δ at 60 ° C is low. From this result, it was confirmed that both rolling resistance and wet grip performance were excellent.

In other words, in the oil meter 1, it was confirmed that both the rolling resistance and the wet grip performance have a predetermined weight average molecular weight, a Z average molecular weight, a ratio of a Z average molecular weight to a weight average molecular weight, and a softening point temperature. In particular, a decane-modified hydrocarbon resin such as a weight-locked molecular weight and a softening point temperature within a predetermined range.

Thus, it is a decane-modified hydrocarbon resin which is modified by a predetermined amount of an organic decane compound to modify a hydrocarbon resin containing a predetermined monomer unit in a predetermined ratio, and has a weight average molecular weight and a softening point temperature within a predetermined range. Therefore, it has been confirmed that an increase in the glass transition temperature can be suppressed, and an elastomer composition for a tire excellent in workability and excellent in balance between rolling resistance and wet grip performance can be obtained.

Claims (4)

A hydrocarbon resin modified with decane, which is characterized in that it contains 20 parts by mass of a 1,3-pentadiene monomer unit by using 0.1 part by mass to 10 parts by mass of the organodecane compound represented by the following formula (1). 70% by mass, 4 to 6 carbon atoms of the alicyclic monoolefin monomer unit, 10% by mass to 35% by mass, and 4 to 8% by weight of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms, an alicyclic ring When the amount of the hydrocarbon resin of the aromatic diolefin monomer unit is from 0% by mass to 10% by mass and the aromatic monoolefin monomer unit is from 0% by mass to 40% by mass, 100 parts by mass of the hydrocarbon resin is obtained, and the weight average molecular weight (Mw) is 1,000. In the range of ~8000, the Z average molecular weight (Mz) is in the range of 2000 to 25000, the ratio of the Z average molecular weight to the weight average molecular weight (Mz/Mw) is in the range of 1.0 to 4.5, and the softening point temperature is 80 °C. In the range of 110 ° C, X ₃ Si-RF-[R-Si-X ₃ ] _p (1) (in the formula (1), each X system is independent, and is a ruthenium atom-bonding functional group, and each R system is independent Is a divalent or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, and F is a monovalent or polyvalent organic functional group. When F is 1 valence, p is 0, and when F is multivalent, p is At least 1). The decane-modified hydrocarbon resin of claim 1, wherein X is a hydroxyl group or R ¹ -O- (wherein R ¹ is an alkyl group, an alkoxyalkyl group, an aryl group, an aralkyl group having 20 carbon atoms) Or a cycloalkyl group, R is an alkylene group, p is 0 or 1, when p is 0, the F is selected from the group consisting of an amine group, a guanamine group, a hydroxyl group, an alkoxy group, a halogen group, a thio group, Anthracene hydrogen, carboxyl, sulfhydryl, vinyl, allyl, styryl, ureido, epoxy, isocyanate, decyl, epoxypropoxy, and propylene fluorenyl, when p is 1 In the case, F is a divalent polysulfide group of 2 to 20 sulfur atoms. An elastomer composition for a tire, comprising: at least one elastomer, at least one filler, and a hydrocarbon resin modified with decane according to claim 1 or 2. The elastomer composition for a tire according to claim 3, wherein the filler is cerium oxide.