WO2017170839A1 - Silane modified hydrocarbon resin and tire elastomer compound - Google Patents

Abstract

The main purpose of the present invention is to provide a silane modified hydrocarbon resin that has good workability and that realizes a tire elastomer compound that has good balance between rolling resistance and wet grip performance. The present invention achieves the foregoing by providing a silane modified hydrocarbon resin that is obtained by modifying 100 parts by mass of a hydrocarbon resin that contains 20-70% by mass of 1,3-pentadiene monomers, 10-35% by mass of C4-C6 alicyclic monoolefin monomers, 3-30% by mass of C4-C8 acyclic monoolefin monomers, 0-10% by mass of alicyclic diolefin monomers, and 0-40% by mass of aromatic monoolefin monomers, using 0.1-10 parts by mass of an organic silane compound represented by formula (1). The silane modified hydrocarbon resin is characterized in that the weight-average molecular weight (Mw) is in the range of 1000-8000, the Z average molecular weight (Mz) is in the range of 2000-25000, the ratio (Mz/Mw) of the Z average molecular weight with respect to the weight-average molecular weight is in the range of 1.0-4.5, and the softening point temperature is in the range of 80-110°C.

Description

Silane-modified hydrocarbon resin and tire elastomer composition

The present invention relates to a silane-modified hydrocarbon resin that gives an elastomer composition for tires that is excellent in workability and has a good balance of rolling resistance and wet grip performance.

In recent years, automobile tires are strongly required to have low fuel consumption due to environmental problems and resource problems. On the other hand, in terms of safety, for example, improvement in wet grip properties is required. The cross-linked product of the elastomer composition in which silica is added to the elastomer as a filler has a lower rolling resistance when a tire is configured than the cross-linked product of the elastomer composition in which carbon black is mixed. Therefore, a tire excellent in fuel efficiency can be obtained by constituting a tire using a crosslinked product of an elastomer composition blended with silica.

However, even when silica is blended with a conventional elastomer, the affinity between the elastomer and silica is insufficient, and these are easily separated, resulting in poor processability of the elastomer composition before crosslinking. The elastomer cross-linked product obtained by cross-linking this has a problem that the rolling resistance is insufficient when a tire is constituted.

Further, Patent Document 1 discloses that a silane-modified hydrocarbon resin is mixed with an elastomer and used for the purpose of improving the rolling resistance and wet grip property of the tire.

Japanese Patent Laying-Open No. 2015-4074

However, with the silane-modified hydrocarbon resin described in Patent Document 1, it is difficult to improve both wet grip properties and rolling resistance in a well-balanced manner when a tire is produced from an elastomer crosslinked product obtained by adding the silane-modified hydrocarbon resin. There is a problem such as.

The present invention has been made in view of the above problems, and provides a silane-modified hydrocarbon resin that provides an elastomer composition for tires that is excellent in workability and that has an excellent balance of rolling resistance and wet grip performance. The main purpose.

As a result of intensive studies on silane-modified hydrocarbon resins that give an elastomer composition for tires that are excellent in workability and have a good balance between rolling resistance and wet grip performance, the inventors described, for example, in Patent Document 1 Such a conventional silane-modified hydrocarbon resin has a high glass transition temperature (Tg), a weight average molecular weight (Mw), etc., and it is found that this is involved in the reduction of rolling resistance to complete the present invention. It has come.

Thus, according to the present invention, 1,3-pentadiene monomer unit 20 mass% to 70 mass%, alicyclic monoolefin monomer unit 4 to 6 carbon atoms 10 mass% to 35 mass%, carbon number 4-8 acyclic monoolefin monomer units 3 mass% to 30 mass%, alicyclic diolefin monomer units 0 mass% to 10 mass%, and aromatic monoolefin monomer units 0 mass% It is obtained by modifying 100 parts by mass of a hydrocarbon resin containing ˜40% by mass with 0.1 to 10 parts by mass of an organosilane compound represented by the following formula (1). 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 range, softening point temperature is 80 ℃ ~ Silane-modified hydrocarbon resin being in the range of 10 ° C. is provided.

X ₃ Si—R—F— [R—Si—X ₃ ] _p (1)

(In formula (1), each X is independently a silicon atom-bonded functional group, and each R is independently a divalent substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms. F is a monovalent or polyvalent organic functional group. When F is monovalent, p is 0, and when F is polyvalent, p is at least 1.)

X is a hydroxy group or R ¹ —O— (wherein R ¹ is an alkyl group, alkoxyalkyl group, aryl group, aralkyl group or cycloalkyl group of up to 20 carbon atoms); When R is an alkylene group, p is 0 or 1, and p is 0, F is an amino group, an amide group, a hydroxy group, an alkoxy group, a halo group, a mercapto group, a hydrosilyl group, a carboxy group, Selected from acyl, vinyl, allyl, styryl, ureido, epoxy, isocyanato, hydrazino, glycidoxy, and acryloxy, and when p is 1, F is 2 to 20 sulfur atoms The divalent polysulfide group is preferable.

Further, according to the present invention, there is provided a tire elastomer composition comprising at least one elastomer, at least one filler, and the above-mentioned silane-modified hydrocarbon resin.

It is preferable that the filler is silica.

The present invention has the effect of providing a silane-modified hydrocarbon resin that provides a tire elastomer composition that is excellent in workability and has a good balance between rolling resistance and wet grip performance.

The present invention relates to a silane-modified hydrocarbon resin and a tire elastomer composition using the same.
Hereinafter, the silane-modified hydrocarbon resin and the tire elastomer composition of the present invention will be described in detail.

A. Silane-modified hydrocarbon resin The silane-modified hydrocarbon resin of the present invention comprises 1,3-pentadiene monomer unit 20% by mass to 70% by mass and C 4-6 alicyclic monoolefin monomer unit 10% by mass. 35 mass%, 4 to 8 carbon acyclic monoolefin monomer unit 3 mass% to 30 mass%, alicyclic diolefin monomer unit 0 mass% to 10 mass%, and aromatic monoolefin Obtained by modifying 100 parts by mass of a hydrocarbon resin containing 0 to 40% by mass of monomer units with 0.1 to 10 parts by mass of an organosilane compound represented by the following formula (1) 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 Within 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—R—F— [R—Si—X ₃ ] _p (1)

(In formula (1), each X is independently a silicon atom-bonded functional group, and each R is independently a divalent substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms. F is a monovalent or polyvalent organic functional group. When F is monovalent, p is 0, and when F is polyvalent, p is at least 1.)

According to the present invention, the silane-modified hydrocarbon resin is obtained by modifying a hydrocarbon resin containing the predetermined monomer unit at a predetermined ratio with a predetermined amount of an organic silane compound, and having a predetermined weight average molecular weight, Z Elastomer composition for tire having excellent workability and excellent balance of rolling resistance and wet grip performance by having properties such as average molecular weight, ratio of Z average molecular weight to weight average molecular weight, softening point temperature, etc. Can be obtained.
Here, by using the silane-modified hydrocarbon, it is not clear why the elastomer composition for a tire excellent in workability and excellent in the balance of rolling resistance and wet grip performance can be obtained, but the following It is guessed as follows.
That is, the silane-modified hydrocarbon resin of the present invention has a weight average molecular weight (Mw) and glass by using the above-mentioned predetermined monomer units and a proportion of the hydrocarbon resin and further having the above-mentioned predetermined characteristics. The transition temperature can be reasonably low.
Therefore, when the silane-modified hydrocarbon resin of the present invention is mixed with an elastomer or the like to form an elastomer composition, the silane-modified hydrocarbon resin has excellent compatibility with the elastomer. For example, for the obtained elastomer composition, The loss factor tan δ at 60 ° C. of the cross-linked product can be lowered, and the loss factor tan δ at 0 ° C. can be appropriately increased.
As a result, when a tire is manufactured using such an elastomer composition, it is possible to form a tire having an excellent balance between rolling resistance and wet grip performance.
In addition, since the silane-modified hydrocarbon resin is excellent in compatibility with the elastomer, for example, uniform mixing with the elastomer is facilitated, so that the processing characteristics can be improved.
Furthermore, the silane-modified hydrocarbon resin is modified with a predetermined amount of an organic silane compound and includes a predetermined amount of a silane-modified site, thereby increasing the apparent surface area of silica by increasing the dispersibility of silica, for example, and an elastomer. It is possible to promote the bonding of silica and reduce the loss coefficient tan δ at 60 ° C., and to obtain an elastomer composition capable of producing a tire excellent in rolling resistance.
As described above, the silane-modified hydrocarbon resin obtained by modifying the hydrocarbon resin containing the predetermined monomer unit at a predetermined ratio with a predetermined amount of the organic silane compound is excellent in workability, rolling resistance and wet grip. The tire elastomer composition having an excellent balance of performance can be provided.

The silane-modified hydrocarbon resin of the present invention is a modified product of a hydrocarbon resin with an organic silane compound.
Hereinafter, a hydrocarbon resin before being modified with an organic silane compound (hereinafter, simply referred to as “pre-modified resin”), an organic silane compound and a silane-modified hydrocarbon resin to be modified (hereinafter simply referred to as “modified resin”). There are cases where this may occur).

1. Hydrocarbon Resin The hydrocarbon resin is a raw material resin that has not been modified with an organosilane compound, and is an alicyclic monocyclic monomer unit having a 1,3-pentadiene monomer unit content of 20% to 70% by mass and 4 to 6 carbon atoms. Olefin monomer units 10 mass% to 35 mass%, C 4-8 acyclic monoolefin monomer units 3 mass% to 30 mass%, alicyclic diolefin monomer units 0 mass% to 10 mass% And 0 to 40% by mass of an aromatic monoolefin monomer unit.
In addition, the content rate of the said monomer unit is the same also in modified resin, and the suitable range of the said content rate is the same as that of resin before modification | denaturation.

The content of the 1,3-pentadiene monomer unit in the resin before modification may be within a range of 20% by mass to 70% by mass, and preferably within a range of 25% by mass to 69% by mass. In particular, 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 content is within the above-described range, the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance. Because it can.
The cis / trans isomer ratio in 1,3-pentadiene is not particularly limited and may be any ratio.

The alicyclic monoolefin having 4 to 6 carbon atoms is a hydrocarbon compound having 4 to 6 carbon atoms having one ethylenically unsaturated bond and a non-aromatic ring structure in its molecular 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 resin before modification may be in the range of 10% by mass to 35% by mass, and in the range of 13% by mass to 34% by mass. In particular, the content 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. When the content is within the above-described range, the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance. Because it can.
In the alicyclic monoolefin having 4 to 6 carbon atoms, the ratio of each of the corresponding compounds may be any ratio, and is not particularly limited, but preferably contains at least cyclopentene, and has 4 to 6 carbon atoms. The proportion of cyclopentene in the alicyclic monoolefin is more preferably 50% by mass or more.

The acyclic monoolefin having 4 to 8 carbon atoms is a chain hydrocarbon compound having 4 to 8 carbon atoms having one ethylenically unsaturated bond in its molecular structure and no ring structure. Specific examples of the acyclic monoolefin having 4 to 8 carbon atoms include butenes such as 1-butene, 2-butene and isobutylene (2-methylpropene); 1-pentene, 2-pentene, 2-methyl-1 -Pentenes such as butene, 3-methyl-1-butene, 2-methyl-2-butene; hexenes such as 1-hexene, 2-hexene, 2-methyl-1-pentene; 1-heptene, 2-heptene Heptenes such as 2-methyl-1-hexene; 1-octene, 2-octene, 2-methyl-1-heptene, diisobutylene (2,4,4-trimethyl-1-pentene and 2,4,4- Octenes such as 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, and in the range of 3% by mass to 25% by mass. In particular, it is preferably in the range of 3% by mass to 22% by mass, and more preferably in the range of 3% by mass to 20% by mass. When the content is within the above-described range, the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance. Because it can.
In the acyclic monoolefin having 4 to 8 carbon atoms, the ratio of each of the corresponding compounds (including isomers) may be any ratio, and is not particularly limited. However, at least 2-methyl-2-butene, Preferably, at least one selected from the group consisting of isobutylene and diisobutylene is included, and the total amount of 2-methyl-2-butene, isobutylene and diisobutylene occupies in the acyclic monoolefin having 4 to 8 carbon atoms The ratio is more preferably 50% by mass or more.

The resin before modification may contain an alicyclic diolefin as a raw material.
An 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 diolefin include multimers of cyclopentadiene such as cyclopentadiene and dicyclopentadiene, and multimers of methylcyclopentadiene and methylcyclopentadiene.
The content of the alicyclic diolefin monomer unit in the resin before modification may be in the range of 0% by mass to 10% by mass, and preferably in the range of 0% by mass to 7% by mass. In particular, 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 content is within the above-described range, the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance. Because it can.

The resin before modification may contain an aromatic monoolefin monomer unit in its raw material.
An aromatic monoolefin is an aromatic compound having one ethylenically unsaturated bond in its molecular structure. Specific examples of the aromatic monoolefin include styrene, α-methylstyrene, vinyl toluene, indene, coumarone and the like.
The content of the aromatic monoolefin monomer unit in the resin before modification 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, In particular, it is preferably in the range of 0% by mass to 30% by mass, and particularly preferably in the range of 0% by mass to 28% by mass. When the content is within the above-described range, the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance. Because it can.

Resin before modification is 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 In addition to diolefin monomer units and aromatic monoolefin monomer units, a modified hydrocarbon resin is obtained that provides an elastomer composition for tires that is excellent in workability and has a good balance of rolling resistance and wet grip performance. Other monomer units may be included within the range that can be achieved.
Other monomers used for constituting such other monomer units may be compounds having addition polymerizability that can be addition copolymerized with 1,3-pentadiene or the like other than the aforementioned monomers. There is no particular limitation. Examples of the other monomers include carbon numbers other than 1,3-pentadiene such as 1,3-butadiene, 1,2-butadiene, isoprene, 1,3-hexadiene, and 1,4-pentadiene. An unsaturated monoolefin having 7 or more carbon atoms such as cycloheptene; an acyclic monoolefin having 4 to 8 carbon atoms such as ethylene, propylene and nonene.
However, the content of the other monomer units in the resin before modification in the resin before modification is not particularly limited as long as the modified hydrocarbon resin having the predetermined characteristics can be obtained. Usually, it is in the range of 0% by mass to 30% by mass, preferably in the range of 0% by mass to 25% by mass, and more preferably in the range of 0% by mass to 20% by mass. This is because the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires that is excellent in processability and excellent in the balance between rolling resistance and wet grip performance.

The method for producing the pre-modification resin is not particularly limited as long as the polymerizable component (monomer mixture A) having a monomer capable of constituting the above-described monomer unit is suitably subjected to addition polymerization. For example, the resin before modification can be obtained by addition polymerization using a Friedel-Crafts type cationic polymerization catalyst. As a method suitably used for producing the pre-modified resin, the following aluminum halide (A), halogenated hydrocarbon (B1) in which a halogen atom is bonded to a tertiary carbon atom, and a carbon-carbon bond are used. A combination of a halogenated hydrocarbon (B) selected from the group consisting of a halogenated hydrocarbon (B2) in which a halogen atom is bonded to a carbon atom adjacent to the saturated bond is used as a polymerization catalyst, and 1,3-pentadiene 20% by mass 70 mass%, C 4-6 alicyclic monoolefin 10 mass% -35 mass%, C 4-8 acyclic monoolefin 3 mass% -30 mass%, alicyclic diolefin 0 mass And a method having a polymerization step of polymerizing the monomer mixture A containing 10% by mass to 10% by mass and 0% by mass to 40% by mass of the aromatic monoolefin.

Specific examples of the aluminum halide (A) include aluminum chloride (AlCl ₃ ) and aluminum bromide (AlBr ₃ ). Of these, aluminum chloride is preferably used from the viewpoint of versatility.
The amount of aluminum halide (A) used is not particularly limited, but is preferably in the range of 0.05 to 10 parts by mass, more preferably 100 parts by mass of the polymerizable component (monomer mixture A). It is within the range of 0.1 to 5 parts by mass.

By using the halogenated hydrocarbon (B) in combination with the aluminum halide (A), the activity of the polymerization catalyst becomes extremely good.
Specific examples of the halogenated hydrocarbon (B1) in which a halogen atom is bonded to a tertiary carbon atom include t-butyl chloride, t-butyl bromide, 2-chloro-2-methylbutane, and triphenylmethyl chloride. . Among these, t-butyl chloride is particularly preferably used because it has an excellent balance between activity and ease of handling.
Examples of the unsaturated bond in the halogenated hydrocarbon (B2) in which a halogen atom is bonded to a carbon atom adjacent to the carbon-carbon unsaturated bond include a carbon-carbon double bond and a carbon-carbon triple bond, and an aromatic ring It also includes a carbon-carbon conjugated double bond in Specific examples of such compounds include benzyl chloride, benzyl bromide, (1-chloroethyl) benzene, allyl chloride, 3-chloro-1-propyne, 3-chloro-1-butene, 3-chloro-1-butyne, Examples include cinnamon chloride. Among these, benzyl chloride is preferably used because it is excellent in balance between activity and ease of handling. In addition, halogenated hydrocarbon (B) may be used by 1 type, or may be used in combination of 2 or more types.
The amount of the halogenated hydrocarbon (B) used is preferably in the range of 0.05 to 50, more preferably in the range of 0.1 to 10, as a molar ratio to the aluminum halide (A).

In performing the polymerization reaction, the order of adding each component of the monomer mixture and the polymerization catalyst to the polymerization reactor is not particularly limited, and may be added in any order, but the polymerization reaction is well controlled, From the viewpoint of more accurately controlling the weight average molecular weight and the like, after adding the monomer mixture and a part of the components of the polymerization catalyst to the polymerization reactor and starting the polymerization reaction, the remainder of the polymerization catalyst is subjected to the polymerization reaction It is preferable to add to the vessel.

In producing the pre-modification resin, it is preferable to first mix the aluminum halide (A) and the alicyclic monoolefin. This is because by subjecting the aluminum halide (A) and the alicyclic monoolefin to contact treatment, gel formation can be prevented, and a pre-modified resin in which the weight average molecular weight and the like are accurately controlled can be obtained.

The amount of the alicyclic monoolefin mixed with the aluminum halide (A) is preferably at least 5 times (mass ratio) the amount of the aluminum halide (A). If the amount of the alicyclic monoolefin is too small, the effect of preventing gel formation may be insufficient. The mass ratio of alicyclic monoolefin to aluminum halide (A) is preferably 5: 1 to 120: 1, more preferably 10: 1 to 100: 1, and even more preferably 15: 1 to 80: 1. . If the alicyclic monoolefin is used in an excessive amount from this ratio, the catalytic activity is lowered and the polymerization may not proceed sufficiently.

When mixing the aluminum halide (A) and the alicyclic monoolefin, the charging order is not particularly limited, and the aluminum halide (A) may be charged into the alicyclic monoolefin, and conversely, An alicyclic monoolefin may be introduced into the aluminum halide (A). Since mixing usually involves exotherm, an appropriate diluent can also be used. As the diluent, a solvent described later can be used.

After preparing a mixture M of an aluminum halide (A) and an alicyclic monoolefin as described above, a mixture a containing at least 1,3-pentadiene and an acyclic monoolefin is mixed with the mixture M. It is preferable to do. The mixture a may contain an alicyclic diolefin.
The preparation method of the mixture a is not particularly limited, and each of the pure compounds may be mixed to obtain the target mixture a. For example, a mixture containing the target monomer derived from a fraction of a naphtha decomposition product May be used to obtain the desired mixture a. For example, in order to incorporate 1,3-pentadiene or the like into the mixture a, the C5 fraction after extraction of isoprene and cyclopentadiene (including its multimer) can be preferably used.
It is preferable to further mix the halogenated hydrocarbon (B) together with the mixture a and the mixture M. There are no particular restrictions on the order of these three parties.

From the viewpoint of better controlling the polymerization reaction, it is preferable to carry out the polymerization reaction by adding a solvent to the polymerization reaction system. The type of the solvent is not particularly limited as long as it does not inhibit the polymerization reaction, but saturated aliphatic hydrocarbons or aromatic hydrocarbons are preferable. Examples of the saturated aliphatic hydrocarbon used as the solvent include n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, and 3-ethylpentane. , 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane, 2,2,4-trimethylpentane, etc. Examples include 5-10 chain saturated aliphatic hydrocarbons; cyclic saturated aliphatic hydrocarbons having 5 to 10 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like. Examples of the aromatic hydrocarbon used as the solvent include aromatic hydrocarbons having 6 to 10 carbon atoms such as benzene, toluene and xylene. A solvent may be used individually by 1 type and may be used as a 2 or more types of mixed solvent. The amount of the solvent used is not particularly limited, but is preferably in the range of 10 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the polymerizable component (monomer mixture A), and 50 parts by weight to More preferably, it is in the range of 500 parts by weight. 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 the C5 fraction is added to the polymerization reaction system, and the addition polymerizable component is a single amount. It can be used as a component of the body mixture, and the non-addition polymerizable component can be used as a solvent.

The polymerization temperature for carrying out the polymerization reaction is not particularly limited, but is preferably in the range of −20 ° C. to 100 ° C., and preferably in the range of 0 ° C. to 75 ° C. If the polymerization temperature is too low, the polymerization activity may be lowered and productivity may be inferior. If the polymerization temperature is too high, controllability such as the weight average molecular weight of the resin before modification may be inferior. The pressure for performing the polymerization reaction may be atmospheric pressure or increased pressure. The polymerization reaction time can be appropriately selected, but is usually selected within the range of 10 minutes to 12 hours, preferably 30 minutes to 6 hours.

The polymerization reaction can be stopped by adding a polymerization terminator such as methanol, an aqueous sodium hydroxide solution or an aqueous ammonia solution to the polymerization reaction system when a desired polymerization conversion rate is obtained. A catalyst residue insoluble in the solvent, which is generated when a polymerization terminator is added to deactivate the polymerization catalyst, may be removed by filtration or the like. After termination of the polymerization reaction, the unreacted monomer and solvent are removed, and the oligomer component having a low molecular weight is removed by steam distillation or the like, followed by cooling to obtain a solid unmodified resin.

2. Organic Silane Compound The organic silane compound is represented by the following formula (1).

X ₃ Si—R—F— [R—Si—X ₃ ] _p (1)

(In formula (1), each X is independently a silicon atom-bonded functional group, and each R is independently a divalent substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms. F is a monovalent or polyvalent organic functional group. When F is monovalent, p is 0, and when F is polyvalent, p is at least 1.)

X in the formula (1) may be a silicon atom-bonded functional group, and can be, for example, a group represented by hydroxy or R ¹ —O—. Here, the silicon atom-bonded functional group means a functional group bonded to a silicon atom.
R ¹ is an alkyl group, alkoxyalkyl group, aryl group, aralkyl group or cycloalkyl group of up to 20 carbon atoms, preferably up to 10 carbon atoms, especially 1 to 5 carbon atoms. It is preferable.
In the present invention, it is preferable that X is an alkoxyalkyl group from the viewpoint of dispersibility of silica. This is because the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires excellent in wet grip performance.

R in the formula (1) may be independently a divalent substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms, preferably up to 10 carbon atoms, particularly 1 to 5 carbon atoms. An alkylene group of carbon atoms is preferred. This is because when R is the hydrocarbon group, the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires excellent in wet grip performance.

F in the formula (1) is a monovalent or polyvalent organic functional group and serves as a direct or indirect binding site with the resin before modification.
As such an organic functional group F, when p is 0, for example, an amino group, an amide group, a hydroxy group, an alkoxy group (usually up to 20 carbon atoms), a halo group, a mercapto group, a hydrosilyl group, A group selected from a carboxy group, an acyl group (usually up to 20 carbon atoms), a vinyl group, an allyl group, a styryl group, a ureido group, an epoxy group, an isocyanato group, a hydrazino group, a glycidoxy group, and an acryloxy group be able to.
When p is 1, the organic functional group F in the formula (1) can be, for example, a divalent polysulfide group having 2 to 20 sulfur atoms.
In the present invention, among them, the organic functional group F is preferably a vinyl group, a mercapto group, a polysulfide group, or an amino group. This is because the organic functional group F is easy to modify the silane of the resin before modification.

As specific examples of such an organic silane compound, for example, those mentioned as the bifunctional organic silane crosslinking agent described in JP-A-2015-4074 can be used.
In the present invention, the organosilane compound is preferably 3-aminopropyltriethoxysilane, bis [3- (triethoxysilyl) propyl] tetrasulfide, or the like. This is because the silane compound is excellent in reactivity with the resin before modification.

In addition, the organosilane compound may include only one type, or may be a mixture of two or more types.

The content of the organic silane compound in the silane-modified hydrocarbon resin of the present invention, that is, the content of the organic silane compound bonded to 100 parts by weight of the hydrocarbon resin as the pre-modified resin is 0.1 parts by mass to It may be in the range of 10 parts by weight, preferably in the range of 0.1 to 9 parts by weight, more preferably in the range of 0.1 to 8 parts by weight, particularly The content is preferably in the range of 0.1 to 7 parts by mass. When the content is within the above-described range, the silane-modified hydrocarbon resin of the present invention can provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance. Because it can.

As the silane modification method of the pre-modification resin using the above-mentioned organosilane compound, a modified hydrocarbon resin having a silane structure (—R—SiX ₃ ) bonded to the unmodified resin via the organic functional group F of the organosilane compound. Any method can be used as long as it can be obtained.
As such a silane modification method, a known method can be used as appropriate.
Specifically, as the silane modification reaction, by mixing a pre-modified resin, an organic silane compound and a peroxide initiator, free peroxide is generated in the pre-modified resin by the peroxide initiator. Can be used, for example, a method of reacting an organic functional group F with an organic silane compound, a method of mixing an organic silane compound with a pre-modification resin having an active terminal, and the like.
In such a silane modification reaction, when the organic functional group F is a polysulfide group, for example, the polysulfide moiety is cleaved and the terminal sulfur atom of the cleavage site is bonded to the resin before modification. Can do.

In the silane modification method, the amount of the organic silane compound added to the pre-modified resin is not particularly limited as long as it can bind a desired amount of the organic silane compound. For example, the organic silane in the silane-modified hydrocarbon resin The amount can be the same as or more than the compound content.
The reaction conditions in the silane modification method using free radicals described above are not particularly limited as long as a desired amount of organosilane compound can be bonded to the resin before modification. For example, the reaction temperature may be 0 ° C. to 200 ° C. and the reaction time may be 5 minutes to 20 hours.
Moreover, the said silane modification method can also be performed in an organic solvent, for example.
Such an organic solvent may be the same as the solvent that can be used for the polymerization reaction of the pre-modification resin described in the section “1. Hydrocarbon resin”. The silane modification method may be, for example, a method in which silane modification is performed in a solvent used in polymerization of a resin before modification.

The peroxide initiator is not particularly limited as long as it can bind a desired amount of an organic silane compound to the pre-modification resin. For example, inorganic peroxide such as sodium persulfate, diisopropylbenzene hydroperoxide, etc. Known peroxide initiators such as organic peroxides can be used.
As such inorganic peroxide, organic peroxide, etc., for example, those described in JP-A-2004-285230 can be used.
The amount of the peroxide initiator used is not particularly limited as long as a desired amount of the organosilane compound can be bonded to the pre-modification resin, and is appropriately set depending on the amount of the organosilane compound added. .

The silane modification method may be a method in which an organic silane compound is bonded to a resin before modification via a known silane coupling agent (excluding those corresponding to the organic silane compound) as necessary. . In addition, about the method of couple | bonding a silane coupling agent with resin before modification | denaturation, it can be made to be the same as that of the above-mentioned silane modification method.
As the silane coupling agent, for example, a bifunctional silane coupling agent having a vinyl group and a reactive functional group that can be bonded to the organic functional group F of the organic silane compound can be used.
About the said functional group for reaction, it can set suitably according to the organic functional group F of an organosilane compound.
For example, when the organic functional group F is an amino group or the like, a hydroxy group, a carboxy group, an amino group, a ureido group, a glycidoxy group, a halo group, a sulfonic acid group, or the like may be used as the reactive functional group. it can. Further, when the organic functional group F is the hydroxy group or the like mentioned as an example of the functional group for reaction, an amino group or the like can be used as the functional group for reaction.
In addition, about the bifunctional silane coupling agent which has such a vinyl group and the functional group for reaction, it can select suitably from a well-known silane coupling agent.
Moreover, what is necessary is just to set suitably the compounding quantity of the silane coupling agent used as a spacer between such an organic silane compound and resin before modification in the range which does not inhibit the expression of the effect of this invention.
Examples of the method for bonding the pre-modified resin to which the silane coupling agent is bonded and the organic silane compound include a method in which the pre-modified resin to which the silane coupling agent is bonded and the organic silane compound are mixed and heat-treated. Can do.
As the heat treatment conditions, for example, the temperature can be set within a range of 50 ° C. to 300 ° C. for 5 minutes to 20 hours.
In the above heat treatment, a diluent, an antigelling agent, a reaction accelerator and the like may be present as necessary.
Such a diluent may be the same as the solvent that can be used for the polymerization reaction of the pre-modification resin described in the section “1. Hydrocarbon resin”. The heat treatment may be performed, for example, in a solvent used in the polymerization of the resin before modification.

When the organic functional group F of the organosilane compound is an amino group, an amide group, a hydroxy group, a carboxy group, a mercapto group, a vinyl group, an allyl group, a styryl group, a ureido group, a hydrazino group, an acryloxy group, or a halo group, The silane modification method may be a method of bonding the organic silane compound to the resin before modification by reacting an organic functional group F of the organic silane compound with an acidic group such as a carboxyl group contained in the resin before modification. .
As for the acidic group, an acidic group introduced into the resin before modification by using a polymerizable component (monomer mixture A) containing a monomer having an acidic group may be used. The acidic group introduced by doing so may be used.
Here, as a method of acid-modifying the resin before modification, a known method can be used. For example, when introducing a carboxyl group as an acidic group, the resin before modification and an unsaturated carboxylic acid are mixed and heated. The method of processing can be mentioned.
Examples of unsaturated carboxylic acids used for introducing carboxyl groups include Diels-Alder adducts of conjugated dienes such as maleic acid and α, β-unsaturated dicarboxylic acids having 8 or less carbon atoms.
Moreover, what is necessary is just to set suitably the compounding quantity of acid modifiers, such as unsaturated carboxylic acid introduce | transduced in order to carry out acid modification of such resin before a modification | denaturation, in the range which does not inhibit expression of the effect of this invention.
As the reaction conditions for the acid modification reaction, for example, the reaction may be performed at a temperature in the range of 50 ° C. to 300 ° C. for 5 minutes to 20 hours.
In the acid modification reaction, a diluent, an antigelling agent, a reaction accelerator and the like may be present as necessary.
Examples of the reaction for bonding an acidic group and an organic silane compound include a method in which a resin before modification or a resin before modification after acid modification and an organic silane compound are mixed and heat-treated. About the method of heat-processing, it can be made to be the same as that of the heat processing method which couple | bonds the resin before modification | denaturation which the above-mentioned silane coupling agent couple | bonded, and an organosilane compound, for example.

3. Silane-modified hydrocarbon resin The weight-average molecular weight (Mw) of the silane-modified hydrocarbon resin is not particularly limited as long as it is within the range of 1,000 to 8,000. Is preferably in the range of 1,000, and more preferably in the range of 1,400 to 4,500. This is because, when the weight average molecular weight (Mw) is within the above range, the silane-modified hydrocarbon resin can be excellent in compatibility with the elastomer. Further, as a result, the silane-modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. for the crosslinked product of the elastomer composition and can be excellent in rolling resistance. .
In addition, since the weight average molecular weight (Mw) is within the above range, the silane-modified hydrocarbon resin can easily increase the loss coefficient tan δ at 0 ° C. and has excellent rolling resistance. Because you can.

The Z-average molecular weight (Mz) of the silane-modified hydrocarbon resin is not particularly limited as long as it is in the range of 2,000 to 25,000, but in particular, in the range of 3,000 to 20,000. In particular, it is preferably in the range of 4,000 to 1,5000. This is because, when the Z average molecular weight (Mz) is within the above range, the silane-modified hydrocarbon resin can be excellent in compatibility with the elastomer. Further, as a result, the silane-modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. for the crosslinked product of the elastomer composition and can be excellent in rolling resistance. .

In the present invention, the weight average molecular weight (Mw) and the Z average molecular weight (Mz) of the silane-modified hydrocarbon resin are determined as polystyrene-converted values measured by high performance liquid chromatography.
More specifically, the measurement of the weight average molecular weight and the Z average molecular weight uses “HLC-8320GPC” manufactured by Tosoh Corporation as a measuring apparatus, and a column in which three “TSKgel SuperMultipore HZ” manufactured by Tosoh Corporation are connected. , Using tetrahydrofuran as a solvent, it can be measured at 40 ° C. and a flow rate of 1.0 mL / min.

The ratio of the Z average molecular weight to the weight average molecular weight (Mz / Mw) of the silane-modified hydrocarbon resin is not particularly limited as long as it is in the range of 1.0 to 4.5. It is preferably in the range of 0 to 4.0, more preferably in the range of 1.0 to 3.5. This is because, when the ratio is within the above-described range, the silane-modified hydrocarbon resin can have excellent compatibility with the elastomer. As a result, the silane-modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. for the cross-linked product of the elastomer composition and can be excellent in wet grip performance. is there.

The softening point of the silane-modified hydrocarbon resin is not particularly limited as long as it is in the range of 80 ° C. to 110 ° C. Among them, the softening point is preferably in the range of 85 ° C. to 110 ° C. It is preferably within the range of 90 ° C to 110 ° C. This is because, when the softening point is within the above range, the silane-modified hydrocarbon resin can be excellent in compatibility with the elastomer. Further, as a result, the silane-modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. for the crosslinked product of the elastomer composition and can be excellent in rolling resistance. .
Moreover, since the softening point is within the above-mentioned range, the silane-modified hydrocarbon resin can easily increase the loss coefficient tan δ at 0 ° C. and can have excellent wet grip performance. It is.
The softening point in the present invention is a value measured according to JIS K 6863 for a modified hydrocarbon resin, for example.

The glass transition temperature of the silane-modified hydrocarbon resin is not particularly limited as long as it has excellent compatibility with the elastomer, and can be, for example, in the range of 30 ° C. to 60 ° C., However, it is preferably in the range of 35 ° C to 60 ° C, and particularly preferably in the range of 40 ° C to 60 ° C. This is because, when the glass transition temperature is within the above range, the silane-modified hydrocarbon resin can be excellent in compatibility with the elastomer. As a result, for example, it is easy to lower the loss coefficient tan δ of the elastomer composition at 60 ° C., and it is excellent in workability and rolling resistance, and loss at 0 ° C. It is easy to increase the coefficient tan δ, and the wet grip performance can be improved.
For this reason, when the glass transition temperature is within the above range, it is possible to provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance.
In addition, the glass transition temperature in this invention can be measured on temperature increase rate 10 degree-C / min conditions by differential scanning calorimetry (DSC), for example. Moreover, as a measuring device, Pyris1 DSC (made by Perkin Elmer) can be used, for example.

The silane-modified hydrocarbon resin of the present invention can be used, for example, as a hydrocarbon resin used by mixing with an elastomer in an elastomer composition for various uses.
In the present invention, as described above, the silane-modified hydrocarbon resin can provide an elastomer composition for tires that is excellent in workability and excellent in balance between rolling resistance and wet grip performance.
Therefore, the silane-modified hydrocarbon resin can be suitably used, for example, as a hydrocarbon resin used by mixing with an elastomer in an elastomer composition for a tire, taking advantage of the characteristics.

As a method for producing the silane-modified hydrocarbon resin, 100 parts by mass of a hydrocarbon resin which is a pre-modified resin is modified with 0.1 to 10 parts by mass of an organic silane compound represented by the above formula (1). A method having a denaturation step can be used.
The method of modifying with the organosilane compound, that is, the silane modification method and the like can be the same as the contents described in the above section “2. Organosilane compound”, and thus the description thereof is omitted here. .

B. Next, the tire elastomer composition of the present invention will be described.
The tire elastomer composition of the present invention comprises at least one elastomer, at least one filler, and the above-mentioned silane-modified hydrocarbon resin.

According to the present invention, by using the above-mentioned silane-modified hydrocarbon resin, it is possible to manufacture a tire having excellent workability and excellent balance between rolling resistance and wet grip performance.

The tire elastomer composition of the present invention comprises an elastomer, a filler, and a silane-modified hydrocarbon resin.
Hereafter, each component of the elastomer composition for tires of this invention is demonstrated in detail.

1. Silane-modified hydrocarbon resin The content of the silane-modified hydrocarbon resin is not particularly limited as long as it is excellent in workability and can provide a tire elastomer composition having an excellent balance of rolling resistance and wet grip performance. .
The content can be, for example, in the range of 0.1 to 50 parts by mass, and preferably in the range of 1 to 30 parts by mass, relative to 100 parts by mass of the elastomer. In particular, it is preferably in the range of 1.5 to 20 parts by mass. This is because when the content is within the above-described range, the tire elastomer composition has excellent workability and excellent balance between rolling resistance and wet grip performance.

The silane-modified hydrocarbon resin can be the same as that described in the section “A. Silane-modified hydrocarbon resin”, and the description thereof is omitted here.

2. Elastomer As the elastomer, known elastomers used for tire elastomer compositions can be used.
Examples of such elastomers include natural rubber, polyisoprene rubber, emulsion polymerization styrene-butadiene copolymer rubber, solution polymerization styrene-butadiene copolymer rubber, and polybutadiene rubber (high cis-BR and low cis BR may be used. Further, it may be a polybutadiene rubber containing crystal fibers made of 1,2-polybutadiene polymer), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, acrylonitrile- Examples thereof include butadiene copolymer rubber and acrylonitrile-styrene-butadiene copolymer rubber.
In addition, the said elastomer should just contain at least 1 type, may contain only 1 type, and may mix and use 2 or more types.

3. Filler As said filler, what is generally used for the elastomer composition for tires can be used, for example, carbon black, clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide. , Mica, graphite, aluminum hydroxide, various metal powders, wood powder, glass powder, ceramic powder, etc., inorganic hollow fillers such as glass balloons, silica balloons, polystyrene, polyvinylidene fluoride, polyvinylidene fluoride copolymers, etc. The organic hollow filler which consists of etc. can be mentioned.
Among these fillers, for example, silica, carbon black and the like described in JP-A-2016-30795 can be used.
In the present invention, the filler is preferably silica. This is because when the filler is silica, the tire elastomer composition has excellent wet grip properties.
Moreover, the filler should just contain at least 1 type, may contain only 1 type, and may mix and use 2 or more types.

As content of the said filler, what is excellent in workability and can obtain the elastomer composition for tires which was excellent in the balance of rolling resistance and wet grip performance should just be obtained.
The content can be, for example, in the range of 30 to 250 parts by weight, and is preferably in the range of 30 to 200 parts by weight, particularly in terms of the ratio to 100 parts by weight of the elastomer. The content is preferably in the range of 40 to 150 parts by weight, and more preferably in the range of 50 to 130 parts by weight. This is because when the content is within the above-described range, the tire elastomer composition has excellent processability and wet grip properties.

4). Tire Elastomer Composition The tire elastomer composition of the present invention has an elastomer, a filler, and a silane-modified hydrocarbon resin, but may contain other components as necessary.
Examples of the other components include compounding agents such as a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a crosslinking activator, an anti-aging agent, an activator, a process oil, a plasticizer, a lubricant, and a tackifier. Necessary amount can be blended.
Such other components and their contents can be the same as those described in JP-A-2016-30795, for example.

The manufacturing method of the tire elastomer composition of the present invention may be obtained by kneading each component according to a conventional method, for example, after kneading the component and the elastomer excluding a thermally unstable component such as a crosslinking agent and a crosslinking accelerator, The kneaded product can be mixed with a thermally unstable component such as a crosslinking agent or a crosslinking accelerator to obtain a desired composition. The kneading temperature between the component excluding the thermally unstable component and the elastomer is preferably in the range of 80 ° C. to 200 ° C., more preferably in the range of 120 ° C. to 180 ° C., and the kneading time is preferably 30 ° C. Seconds to 30 minutes. The kneaded product and the thermally unstable component are usually mixed after cooling to 100 ° C. or lower, preferably 80 ° C. or lower.

As a crosslinking method using the tire elastomer composition of the present invention as the tire elastomer crosslinked product, a known crosslinking method can be used. For example, a molding machine corresponding to a desired shape, for example, an extruder or an injection molding machine. Examples of the method include forming by a compressor, a roll, and the like, performing a crosslinking reaction by heating, and fixing the shape as a crosslinked product. In this case, it is possible to perform crosslinking after molding in advance or at the same time as molding. The molding temperature is usually in the range of 10 ° C to 200 ° C, 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., and the crosslinking time is usually in the range of 1 minute to 24 hours, preferably 2 minutes to 12 hours. And particularly preferably within the range of 3 minutes to 6 hours.

In addition, depending on the shape and size of the elastomer crosslinked product for tires, even if the surface is crosslinked, the interior may not be sufficiently crosslinked. May be.

As the heating method, a general method used for crosslinking of the elastomer composition such as press heating, steam heating, oven heating, hot air heating, etc. may be appropriately selected.

Since the tire elastomer composition of the present invention can provide a tire having a good balance between rolling resistance and wet grip performance, it is excellent in low heat buildup and wet grip properties. The elastomer composition of the present invention is preferably used as a material for each part of a tire, such as a cap tread, a base tread, a carcass, a sidewall, and a bead part of the tire, taking advantage of such characteristics. In various tires such as all-season tires, high-performance tires, and studless tires, it can be suitably used for tire parts such as treads, carcass, sidewalls, and bead parts. It can be particularly suitably used as a tread for a fuel-efficient tire.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the part and% in each example are a mass reference | standard unless there is particular notice.

Various measurements were performed according to the following methods.

[Weight average molecular weight, Z average molecular weight and molecular weight distribution]
For the silane-modified hydrocarbon resin as a sample, gel permeation chromatography analysis is performed to determine the weight average molecular weight (Mw) and Z average molecular weight (Mz) in terms of standard polystyrene, and the molecular weight distribution is a ratio of Mz / Mw. Indicated. The gel permeation chromatography analysis uses “HLC-8320GPC” manufactured by Tosoh Corporation as a measuring device, and the column uses three connected “TSKgel SuperMultipore HZ” manufactured by Tosoh Corporation, with tetrahydrofuran as a solvent. , 40 ° C. and a flow rate of 1.0 mL / min.

[Softening point (℃)]
The silane-modified hydrocarbon resin as a sample was measured according to JIS K 6863.

[Mooney viscosity (ML1 + 4)]
A sample elastomer composition was measured according to JIS K 6300-1: 2001 under the following conditions.
Test temperature: 100 ° C
・ Rotor type: L type ・ Testing machine: Shimadzu Mooney Viscometer SMV-300J manufactured by Shimadzu Corporation

[Tensile strength (MPa) and elongation (%)]
About the test piece of the elastomer crosslinked material used as a sample, tensile strength (tensile stress (MPa)) and elongation (elongation (%)) were measured in accordance with JIS K 6251: 2010 under the following conditions.
-Test piece preparation method: After sheet preparation by press vulcanization, punching process-Test piece shape: Dumbbell shape No. 3-Specimen sampling direction: Parallel to line arrangement-Number of test pieces: 3
・ Measurement temperature: 23 ℃
・ Test speed: 500 mm / min
・ Testing machine: TENSOMETER 10k manufactured by ALPHA TECHNOLOGIES
・ Test machine capacity: Load cell type 1kN

[Loss tangent tan δ]
With respect to the test piece of the crosslinked elastomer as a sample, the loss tangent tan δ at 0 ° C. and 60 ° C. was measured under the conditions of dynamic strain 0.5% and 10 Hz under the following measurement conditions according to JIS K 7244-4. . About this characteristic, it showed with the index | exponent which makes a reference | standard sample (after-mentioned comparative example 1) 100.
The higher the loss tangent tan δ at 0 ° C., the better the wet grip performance, and the lower the loss tangent tan δ at 60 ° C., the better the rolling resistance.
Measurement item: Dynamic storage elastic modulus E '
: Dynamic loss modulus E ''
: Loss tangent tan δ
-Sample preparation method: punching from sheet-Specimen shape: length 50 mm x width 2 mm x thickness 2 mm
・ Number of specimens: 1
・ Distance between clamps: 20mm

[Example 1]
A polymerization reactor was charged with a mixture of 47.3 parts of cyclopentane and 28.3 parts of cyclopentene. The temperature was raised to 70 ° C., and then 0.75 part of aluminum chloride was added (mixture M ₁ ).
Subsequently, from 63.6 parts of 1,3-pentadiene, 6.2 parts of isobutylene, 0.1 part of dicyclopentadiene, 0.3 part of C4-C6 unsaturated hydrocarbon, and 5.7 parts of C4-C6 saturated hydrocarbon the mixture a ₁ comprising, maintaining the temperature (70 ° C.) for 60 minutes, was subjected to a continuous polymerization while adding to the polymerization reactor containing the mixture M _1. Thereafter, an aqueous sodium hydroxide solution was added to the polymerization reactor to stop the polymerization reaction. Table 1 summarizes the types and amounts of the components in the polymerization reactor during the polymerization reaction. After removing the precipitate generated by the termination of polymerization by filtration, the obtained polymer solution was charged into a distillation kettle and heated in a nitrogen atmosphere to remove the polymerization solvent and unreacted monomers. Next, the oligomer component having a low molecular weight was distilled off at 240 ° C. or higher while blowing saturated water vapor.

For 100 parts of molten resin, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by BASF) as an antioxidant. 0.2 part is added, and then 2.0 parts of maleic anhydride is added and subjected to addition reaction at 230 ° C. for 1 hour, and then 1.5 parts of 3-aminopropyltriethoxysilane is added as an organic silane compound, The addition reaction was performed at 230 ° C. for 1 hour. Thereafter, the molten resin was taken out from the distillation kettle and allowed to cool to room temperature to obtain the silane-modified hydrocarbon resin of Example 1. About the obtained silane modified hydrocarbon resin of Example 1, the weight average molecular weight, Z average molecular weight, molecular weight distribution, and softening point were measured. These measurement results are summarized in Table 1 below.
The values of organosilane compound (parts) / resin before modification (100 parts) in Table 1 are calculated by using maleic anhydride used for acid modification as part of the raw material of the resin before modification. The addition amount (parts) of the organosilane compound per 100 parts in total of the monomer mixture constituting the pre-modification resin described in 1 and maleic anhydride.

[Example 2]
A hydrocarbon resin was obtained in the same manner as in Example 1 except that the type and amount of components added to the polymerization reactor and the polymerization temperature were changed as shown in Table 1 below. The diisobutylene and the aromatic monoolefin were mixed with 1,3-pentadiene or the like and subjected to polymerization.
Furthermore, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, trade name: Irga) as an antioxidant with respect to 100 parts of the resin in the molten state 0.2 parts of Knox 1010) was added, and 3.0 parts of bis [3- (triethoxysilyl) propyl] tetrasulfide was added as an organic silane compound, followed by addition reaction at 230 ° C. for 1 hour. Thereafter, the molten resin was taken out from the distillation kettle and allowed to cool to room temperature to obtain the silane-modified hydrocarbon resin of Example 2. For the obtained silane-modified hydrocarbon resin of Example 2, the weight average molecular weight, Z average molecular weight, molecular weight distribution, and softening point were measured. These measurement results are summarized in Table 1 below.
The value of organosilane compound (parts) / pre-modification resin (100 parts) in Table 1 is the amount of organosilane compound added per 100 parts of the monomer mixture used as the raw material of the pre-modification resin listed in Table 1 ( Part).

[Examples 3 to 4, Comparative Examples 1 to 4]
Examples 3 to 4 and Comparative Examples 1 to 2 were the same as Example 1 or 2, except that the types and amounts of components added to the polymerization reactor and the polymerization temperature were changed as shown in Table 1 below. 4 silane-modified hydrocarbon resins were obtained. Specifically, in Example 3 and Comparative Example 3, a silane-modified hydrocarbon resin was obtained after acid-modifying the resin before modification in the same manner as in Example 1. In Example 4 and Comparative Example 4, as in Example 2, a silane-modified hydrocarbon resin was produced by directly bonding an organosilane compound to the resin before modification. Furthermore, Comparative Example 1 and Comparative Example 2 obtained an unmodified hydrocarbon resin without performing silane modification with an organic silane compound, respectively.
Incidentally, diisobutylene, aromatic monoolefin and toluene not described in Example 1 or 2 were mixed with 1,3-pentadiene or the like and subjected to polymerization.

[Production and Evaluation of Elastomer Composition and Crosslinked Elastomer]
In a Banbury mixer, 100 parts of solution-polymerized styrene-butadiene rubber (S-SBR) was masticated for 30 seconds, and then 53.0 parts of silica (trade name “Zeosil 1115MP” manufactured by Rhodia), silane coupling agent: bis 7.0 parts of [3- (triethoxysilyl) propyl] tetrasulfide (Degussa, trade name “Si69”) and 5 parts of the silane-modified hydrocarbon resin obtained in Example 1 were added and kneaded for 90 seconds. Silica (Rhodia, trade name “Zeosil 1115MP”) 32.0 parts, zinc oxide 3.0 parts, stearic acid 2.0 parts and anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl ) -P-Phenylenediamine (trade name “NOCRACK 6C” manufactured by Ouchi Shinsei Co., Ltd.) (2.0 parts) was added, kneaded for 90 seconds, and then process oil 25 parts (trade name “Aromax T-DAE” manufactured by Nippon Oil Corporation) were introduced.
Thereafter, the mixture was kneaded at 90 ° C. as a starting temperature, kneaded at 145 ° C. to 155 ° C. for 60 seconds or more (primary kneading), and then the kneaded product was discharged from the mixer.

The obtained kneaded product was cooled to room temperature and then kneaded again (secondary kneading) at 90 ° C. for 2 minutes in a Banbury mixer, and then the kneaded product was discharged from the mixer. The temperature of the kneaded product at the end of kneading was 145 ° C.

Next, with two rolls at 50 ° C., the obtained kneaded product was mixed with 2.0 parts of sulfur and a vulcanization accelerator: N-cyclohexyl-2-benzothiazolylsulfenamide (CBS trade name “NOXELLA CZ-G”). 1.9 parts of Ouchi Shinsei Chemical Industry Co., Ltd.) and 1.9 parts of diphenylguanidine (DPG product name “Noxeller D”, Ouchi Shinsei Chemical Co., Ltd.) are added and kneaded (mixed with vulcanizing agent) After kneading, the sheet-like elastomer composition was taken out.

This elastomer composition was press-crosslinked for 40 minutes at a press pressure of about 8 MPa and a press temperature of 160 ° C., and then aged overnight in a thermostatic chamber at 23 ° C., and then a test piece of 150 mm × 150 mm × 2 mm thick elastomer cross-linked product Was made.

For the elastomer composition and the crosslinked elastomer obtained using the silane-modified hydrocarbon resin obtained in Example 1, the Mooney viscosity of the elastomer composition, the tensile strength (MPa) of the crosslinked elastomer, the elongation (%) and The loss tangent tan δ was measured. The results are shown in Table 1.
For the resulting silane-modified hydrocarbon resins of Examples 2 to 4 and Comparative Examples 1 to 4, respectively, an elastomer composition and a crosslinked elastomer were prepared in the same manner, and the Mooney viscosity of the elastomer composition, the crosslinked elastomer, The tensile strength (MPa), elongation (%), and loss tangent tan δ were measured. The results are shown in Table 1.
The kneading conditions for primary kneading, secondary kneading and vulcanizing agent kneading were as shown below.

(Kneading conditions for primary and secondary kneading)
・ Testing machine: Labo Plast Mill, Banbury mixer B-600 manufactured by Toyo Seiki Seisakusho Co., Ltd.
・ Filling rate: 70-75 vol%
・ Rotor speed: 50rpm
・ Test start set temperature: 90 ℃

(Kneading conditions for vulcanizing agent)
・ Testing machine: Ikeda Machine Industries Co., Ltd. electric heating type high temperature roll machine ・ Roll size: 6φ × 16
-Front roll speed: 24rpm
-Front / rear roll rotation ratio: 1: 1.22
・ Roll temperature: 50 ℃ ± 5 ℃
・ Number of turn-over: Twice left and right ・ Rounding width: Roll interval approx. 0.8mm
・ Number of rounding: 5 times

From Table 1, it was confirmed that the loss tangent tan δ at 0 ° C. was high and the loss tangent tan δ at 60 ° C. was low in the examples. From this result, it was confirmed that both the rolling resistance and the wet grip performance were excellent.
That is, from Table 1, those excellent in both rolling resistance and wet grip performance have characteristics such as predetermined weight average molecular weight, Z average molecular weight, ratio of Z average molecular weight to weight average molecular weight, softening point temperature, etc. For example, it was confirmed that the silane-modified hydrocarbon resin had a weight average molecular weight and a softening point temperature within predetermined ranges.
Thus, a silane in which the hydrocarbon resin containing the predetermined monomer unit in a predetermined ratio is modified with a predetermined amount of an organic silane compound, and the weight average molecular weight, the softening point temperature, and the like are within a predetermined range. By being a modified hydrocarbon resin, an increase in the glass transition temperature can be suppressed, and it is possible to obtain an elastomer composition for tires that is excellent in workability and excellent in the balance between rolling resistance and wet grip performance. It could be confirmed.

Claims (4)

1. 1,3-pentadiene monomer unit 20 mass% to 70 mass%,
   10 to 35% by mass of an alicyclic monoolefin monomer unit having 4 to 6 carbon atoms,
   3 to 30% by mass of an acyclic monoolefin monomer unit having 4 to 8 carbon atoms,
   100 parts by mass of a hydrocarbon resin containing 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 is represented by the following formula (1). Obtained by modification with 0.1 to 10 parts by mass of the organosilane compound to be obtained,
   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,
   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,
   A silane-modified hydrocarbon resin having a softening point temperature in the range of 80 ° C to 110 ° C.
   X ₃ Si—R—F— [R—Si—X ₃ ] _p (1)
   (In formula (1), each X is independently a silicon atom-bonded functional group, and each R is independently a divalent substituted or unsubstituted hydrocarbon group of 1 to 20 carbon atoms. F is a monovalent or polyvalent organic functional group. When F is monovalent, p is 0, and when F is polyvalent, p is at least 1.)
2. X is a hydroxy group or R ¹ —O— (wherein R ¹ is an alkyl group, alkoxyalkyl group, aryl group, aralkyl group or cycloalkyl group of up to 20 carbon atoms);
   R is an alkylene group;
   p is 0 or 1;
   When p is 0, F is an amino group, amide group, hydroxy group, alkoxy group, halo group, mercapto group, hydrosilyl group, carboxy group, acyl group, vinyl group, allyl group, styryl group, ureido group, epoxy. Selected from a group, an isocyanato group, a hydrazino group, a glycidoxy group, and an acryloxy group;
   The silane-modified hydrocarbon resin according to claim 1, wherein when p is 1, F is a divalent polysulfide group having 2 to 20 sulfur atoms.
3. A tire elastomer composition comprising at least one elastomer, at least one filler, and the silane-modified hydrocarbon resin according to claim 1 or 2.
4. The tire elastomer composition according to claim 3, wherein the filler is silica.